Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same

ABSTRACT

Compounds and methods of preparing compounds of the formula: 
     
       
         RZ—CO—CR a R b —(CR c R d ) n —NH—(Y) m —CO—A  (I) 
       
     
     wherein n is an integer from 1 to 15, m is either 0 or 1; R a , R b , R c , and R d  are each a hydrogen or a hydrocarbyl group; Y is CO—(CR e R f ) p , wherein R e  and R f  are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C 6 H 4 —, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group; Z is —O— or —NG—, wherein G is H, C 1 -C 12  alkyl or the radical R; wherein R is                    
     wherein R 1  is hydrogen, C 1 -C 18  alkyl, O, OH, CH 2 CN, C 1 -C 18  alkoxy, C 1 -C 18  hydroxyalkoxy, C 5 -C 12  cycloalkoxy, C 5 -C 12  hydroxycycloalkoxy, C 3 -C 6  alkenyl, C 1 -C 18  alkynyl, C 7 -C 9  phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C 1 -C 4  alkyls, or an aliphatic C 1 -C 8  acyl; R 2  is hydrogen, C 1 -C 8  alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6  are each a hydrogen, C 1 -C 8  alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10  cycloalkyl; and A is either ZR or a hydrocarbyl group, which are useful for stabilizing polymer compositions against photo- and thermal degradation.

This application is a continuation-in-part of U.S. application Ser. No.09/704,793, filed Nov. 3, 2000.

FIELD OF THE INVENTION

This invention relates generally to novel hindered amine lightstabilizers (HALS) and their use as a protectant against ultravioletradiation or light (“UV light”). Also included are concentrates andarticles including such stabilizers, and methods of making all of theabove.

BACKGROUND

It is well known that ultraviolet (“UV”) light or radiation, especiallysunlight, can cause degradation of a variety of materials, especiallypolymeric materials. Often this results in embrittlement or yellowing ofthe materials, which may be in the form of molded articles, extrudedarticles, films, tapes, coatings, or the like. However, this degradationcan be inhibited by the incorporation of light stabilizers in, or on,the polymeric articles. The most commonly used stabilizers areUV-absorbers, hindered amine light stabilizers (“HALS”), and phenolicand non-phenolic antioxidants.

HALS scavenge free radicals formed in polymeric material when thematerial is exposed to UV light. The functional component of the HALSmolecule is typically the 2,2,6,6-tetraalkylpiperidine moiety.Typically, the 2,2,6,6-tetraalkylpiperidine moiety is anchored to acarbonyl or melamine functional group (See, e.g., U.S. Pat. Nos.4,331,586; 3,840,494; Re. 31,342; Re. 30,385; 3,640,928; 4,086,204;4,265,805). Anchoring the 2,2,6,6-tetraalkylpiperidine moiety to acarbonyl or melamine functional group typically lowers the volatilityand extractability of a stabilizer. Low volatility is an importantcharacteristic of light stabilizers in applications where hightemperatures are encountered, which occurs frequently in the processingof thermoplastics and in the curing of thermoset resins and coatings.Often, high temperatures are also present in the end-use applicationsfor the stabilized material. Low volatility helps prevent loss of thestabilizer during processing, curing, and high temperature end uses.Typically, HALS molecules containing the 2,2,6,6-tetraalkylpiperidinegroup anchored to a carbonyl group are made by reacting a2,2,6,6-tetraalkylpiperidin-4-ol or4-amino-2,2,6,6-tetramethylpiperidine with a carboxylic acid chloride orester.

U.S. Pat. Nos. Re. 31,342, 4,021,432 and 4,049,647 disclose a class of1- and 4-substituted piperidines that are stabilizers for organicmaterials. The stabilizers are produced by reacting the corresponding1-substituted piperidinols with acid chlorides, or the corresponding4-substituted piperidines, with a compound introducing a residue intothe 1-position of the piperidine moiety.

U.S. Pat. No. 3,840,494 discloses a polymer composition stabilizedagainst photo- and thermal deterioration by incorporating therein acidesters of 4-piperidinol derivatives in an amount sufficient to preventsuch deterioration. The acid esters of the 4-piperidinol derivatives areprepared by reacting the 4-piperidinol derivative with a carboxylateester in xylene with sodium hydroxide. For example, the reaction of4-hydroxy-2,2,6,6-tetramethylpiperidine with ethyl benzoate produces4-benzoyloxy-2,2,6,6-tetramethylpiperidine.

Similarly, the 2,2,6,6-tetramethylpiperidin-4-ol can be reacted withdiesters or diacid chlorides to produce diester-HALS. Also, the2,2,6,6-tetramethylpiperidin-4-ol can be reacted with a diisocyanate toproduce a diurethane HALS. However, the relatively high cost ofdiisocyanates makes them less practical than diesters when preparingHALS.

Compounds which have an ester functionality at one terminus of ahydrocarbon chain and a urethane functionality at the other terminus ofthe hydrocarbon chain (alkoxycarbonylamino alkanoates) are known forvarious other uses other than light stabilization and can be prepared bya variety of synthetic schemes (See, e.g., Effenberger, F.; Drauz, K.;Foerster, S.; Mueller, W., Chem. Ber., 114(1), 173-89; Dixit, A.;Tandel, S.; Rajappa, S.; Tett. Lett.; 35(33), 6133-4, Duong, et al.,Aust. J. Chem., 29, 2651-61, 1976; Iwaka et al., J. Org. Chem., 31,142-46, 1966; Taub; Hino; J. Chem. Eng. Data, 9, 106, 1964; U.S. Pat.No. 5,300,678 to Merger et al.).

U.S. Pat. No. 5,574,162 discloses 1-hydrocarbyloxy substituted HALS,which also contain reactive functional groups that chemically attach toselected polymer substrates by condensation reactions.

Oligomeric HALS are also known. For example, TINUVIN 622 is acommercially available oligomeric HALS produced by Ciba SpecialtyChemicals Inc. of Hawthorne, N.Y. TINUVIN 622 can be produced by thereaction of dimethyl succinate withN-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol. U.S. Pat. No.4,233,412 discloses condensation and addition polymers wherein therecurrent molecular unit contains a polyalkylpiperidine radical that areuseful as light stabilizers for plastics. In one embodiment thecopolymer is formed by copolymerization or copolycondensation ofpolyalkylpiperidine containing monomers with polyalkylpiperidine freemonomers such as caprolactam.

U.S. Pat. No. 6,271,377 discloses HALS which are substituted on theN-atom by N-alkyloxy moieties containing one to three hydroxyl groups.

U.S. Pat. No. 4,331,586 to Hardy discloses oligomers that contain atleast one piperidyl moiety in the repeating unit for use as lightstabilizers. While providing protection for polymeric materials, such aspolypropylene, polymeric films containing the disclosed oligomeric HALSbecame brittle after exposure to UV light for about 1,700 hours.

HALS compounds may be used individually or in combination with otherlight stabilizers to inhibit photodegradation of polymers. For example,UV light absorbers, such as benzotriazoles and benzophenones, wereinitially used to stabilize polymeric materials and to preventdegradation of such materials from exposure to UV light. Later, it wasdiscovered that HALS compounds were more effective than UV lightabsorbers alone, and thus, UV light absorbers are presently used incombination with at least one HALS compound in most conventionalapplications (See, e.g., U.S. Pat. Nos. 4,740,542; 4,619,956; 5,461,151;5,721,298). Similarly, HALS compounds are often employed in combinationwith other stabilizers, such as antioxidants (See, e.g., U.S. Pat. No.4,722,806). Combining the HALS with another stabilizer may provide apolymeric material with better resistance to weathering.

U.S. Pat. No. 4,619,956 discloses a method of stabilizing a polymerfilm, coating, or molded article against the action of light, moistureand oxygen by incorporating a HALS compound and a tris-aryl-s-triazineUV light absorber into a polymer. Preferably, the HALS compound is a2,2,6,6-tetraalkylpiperidine compound, salt, or metal complex, and theUV light absorber is a tris-aryl-2-triazine of formula

where X, Y, and Z are each aromatic carbocyclic groups, and at least oneof the aromatic groups has a hydroxy group ortho to the point ofattachment to the triazine ring. Each of R¹ to R⁹ is hydrogen, hydroxy,alkyl, alkoxy, sulfonic, carboxy, halo, haloalkyl, or acylamino. Each ofthe UV light absorbers and HALS compound are used in an amount of fromabout 0.01 to 5 percent by weight, but only formulations having equalamounts of UV light absorber and HALS compound are exemplified. Thecompositions are effective in stabilizing the polymeric material, whichdoes not begin to lose gloss or turn yellow until after about 1,000 to2,400 hours of exposure to UV light.

Thus, a need still remains for improved articles, and compositions andmethods of use and preparation thereof, that stabilize polymericmaterials and provide protection from exposure to UV light for extendedperiods of time. The present invention provides such compositions,articles and methods.

SUMMARY OF THE INVENTION

The invention provides a new class of HALS. The HALS of the inventionhave the formula (I):

RZ—CO—CR^(a)R^(b)—(—CR^(c)R^(d))_(n)—NH—(Y)_(m)—CO—A  (I)

wherein n is an integer from 1 to 15, m is either 0 or 1; R^(a), R^(b),R^(c), and R^(d) are each a hydrogen or a hydrocarbyl group; Y isCO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f) are each a hydrogen orhydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C₆H₄—,wherein the substitution pattern on the phenylene group is an ortho,meta, or para substitution pattern and one or more of the hydrogens ofthe phenylene group may be substituted by a hydrocarbyl group or afunctional group; Z is —O— or —NG—, wherein G is H, C₁-C₁₂ alkyl or theradical R; wherein R is

wherein R¹ is hydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy,C₁-C₁₈ hydroxyalkoxy, C₁-C₁₂ cycloalkoxy, C₁-C₁₂ hydroxycycloalkoxy,C₃-C₆ alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted orsubstituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphaticC₁-C₈ acyl; R² is hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal Rmoieties, which together with the carbon to which they are attached forma C₅-C₁₀ cycloalkyl; and A is either ZR or a hydrocarbyl group.

In one embodiment R¹ is a H, C₁-C₄ alkyl, O, OH; C₁-C₁₈ alkoxy, C₁-C₁₈hydroxyalkoxy, C₅-C₁₂ cycloalkoxy or C₅-C₁₂ hydroxycycloalkoxy, R² is H,or C₁-C₄ alkyl; R³, R⁴, R⁵, and R⁶ are each H or C₁-C₄ alkyl; R^(a),R^(b), R^(c), and R^(d), are each a hydrogen, aromatic, or C₁-C₄ alkyl;and n is from 4 to 1. In another embodiment R¹ is H or CH₃; R³, R⁴, R⁵,and R⁶ are each CH₃; R² is hydrogen; R^(a), R^(b), R^(c) and R^(d) areeach a hydrogen; Z is —O—; m is 0 or 1; and n is and integer from 4 to10.

The invention also provides a method of forming the HALS of theinvention. The HALS of the invention may be prepared by combining one ormore multi-functional carbonyl compounds of general structure:

DO—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—B

wherein n is an integer from 1 to 15, m is either 0 or 1; R^(a), R^(b),R^(c), and R^(d), are each a hydrogen or a hydrocarbyl group; Y isCO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f) are each a hydrogen orhydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C₆H₄—,wherein the substitution pattern on the phenylene group is an ortho,meta, or para substitution pattern and wherein one or more of thehydrogens of the phenylene group may be substituted by a hydrocarbylgroup or a functional group; D is a hydrocarbyl group; and B is eitherOD or D; with one or more 1-substituted piperidin-4-ol or4-aminopiperidines of general structure

wherein Z is OH or NHG, wherein G is as defined above; R¹ is hydrogen,C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy, C₃-C₆ alkenyl, C₁-C₁₈ alkynyl,C₇-C₉ phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl; R² represents hydrogen,C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈alkyl, benzyl or phenethyl, or two geminal R moieties, which togetherwith the carbon to which they are attached form a C₅-C₁₀ cycloalkyl, toform a reaction mixture; reacting the reaction mixture for a sufficienttime to form the compound of formula (I); and recovering the compound offormula (I) from the reaction mixture.

The one or more multifunctional carbonyl compounds may be present in anamount of about 0.025 to 2.5 M and the molar ratio of the one or moremulti-functional carbonyl compounds to the one or more 1-substitutedpiperidin-4-ol or 4-aminopiperidines may be from about 20:1 to 1:5. The4-piperidin-4-ol may be 1,2,2,6,6-pentamethyl-4-piperidinol or2,2,6,6-tetramethyl-4-piperidinol and the multi-functional carbonylcompound may be methyl 6-(methoxycarbonylamino)hexanoate, butyl6-(butoxycarbonylamino) undecanoate, methyl6-(butoxycarbonylamino)undecanoate, butyl6-(methoxycarbonylamino)undecanoate, methyl6-(methoxycarbonylamino)undecanoate, and combinations thereof.

The reaction mixture may include a solvent. The solvent may be one ormore of benzene, toluene, or one or more xylenes. The reaction mixturemay also include a catalyst. The catalyst may be a base catalyst or anacid catalyst. The base catalyst may be methoxide. The acid catalyst maybe a Lewis acid. The Lewis acid may be aluminum trichloride, aluminumtribromide, trimethylaluminum, boron trifluoride, boron trichloride,1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, zinc dichloride, titaniumtetrachloride, titanium (IV) isopropoxide, tin dichloride, tintetrachloride, a tetraalkoxytitanate, and mixtures thereof. The catalystmay be present in an amount of less than about 30 mole percent based onthe molar quantity of the multi-functional carbonyl compound.

In another embodiment the HALS of the invention are prepared from alactam in a single-step by combining one or more lactams of generalstructure:

wherein n is an integer from 1 to 15 and R^(a), R^(b), R^(c), and R^(d)are each a hydrogen or a hydrocarbyl group with one or more carbonylcompounds of general structure

wherein m is either 0 or 1, D is a hydrocarbyl group and B is ahydrocarbyl group or OD and Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) andR^(f) are each a hydrogen or hydrocarbyl group and p is zero or aninteger from 1 to 20 or CO—C₆H₄—, and the substitution pattern on thephenylene group may be an ortho, meta, or para substitution pattern, andone or more of the hydrogens of the phenylene group may be substitutedby a hydrocarbyl group or other functional group; and one or more1-substituted piperidin-4-ol or 4-aminopiperidines of general structure

wherein Z is OH or NHG, wherein G is as defined above; R¹ is hydrogen,C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy, C₃-C₆ alkenyl, C₁-C₁₈ alkynyl,C₇-C₉ phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl; R² represents hydrogen,C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈alkyl, benzyl or phenethyl, or two geminal R moieties, which togetherwith the carbon to which they are attached, form a C₅-C₁₀ cycloalkyl toprovide a reaction mixture; reacting the reaction mixture for asufficient time to form the compound of formula (I); and recovering thecompound of formula (I) from the reaction mixture.

The carbonyl compound may be a dialkyl carbonate, a dialkyl oxalate, adialkyl diester, an alkyl ester, or a mixtures thereof.

The reaction mixture may include a catalyst. The catalyst may be a basecatalyst or an acid catalyst. The base catalyst may be methoxide. Theacid catalyst may be a Lewis acid. The Lewis acid may be aluminumtrichloride, aluminum tribromide, trimethylaluminum, boron trifluoride,boron trichloride, 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, zincdichloride, titanium tetrachloride, titanium (IV) isopropoxide, tindichloride, tin tetrachloride, a tetraalkoxytitanate, and mixturesthereof. The reaction mixture may also include a solvent. The solventmay be one or more of benzene, toluene, or one or more xylenes.

The concentration of lactam may be from about 0.025 to 10 M. The ratioof lactam to carbonyl compound may be from about 2:1 to 1:4; the ratioof lactam to 1-substituted piperidin-4-ol or 4-aminopiperidine may befrom about 1:1; to 1:6; and the catalyst may be present in an amount ofless than about 30 mole percent relative to the amount of carbonylcompound.

In one embodiment n is from 3 to 12 and the catalyst is a base catalystor a Lewis acid. In another embodiment the lactam comprises caprolactamor laurolactam.

The invention also provides for a method of forming a multi-functionalcarbonyl compound having the structure:

DO—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—B

wherein n is an integer from about 1 to 15, m is either 0 or 1; R^(a),R^(b), R^(c), and R^(d) are each a hydrogen or a hydrocarbyl group; Y isCO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f) are each a hydrogen orhydrocarbyl group and p is an integer from about 0 to 20, preferably 0to 10, or CO—C₆H₄—, wherein the substitution pattern on the phenylenegroup is an ortho, meta, or para substitution pattern and one or more ofthe hydrogens of the phenylene group may be substituted by a hydrocarbylgroup or a functional group; D is a hydrocarbyl group; and B is eitherOD or D. The method involves combining one or more lactams of generalstructure

wherein n and R^(a), R^(b), R^(e), and R^(d) are as defined above withone or more carbonyl compounds of general structure

wherein D, B, Y, and m are as defined above; and a Lewis acid catalystto provide a reaction mixture; reacting the reaction mixture for asufficient time to produce the multi-functional carbonyl compound; andrecovering the multi-functional carbonyl compound from the reactionmixture.

In one embodiment n is from about 3 to 12. The Lewis acid catalyst maybe aluminum trichloride, aluminum tribromide, trimethylaluminum, borontrifluoride, boron trichloride, zinc dichloride, titanium tetrachloride,titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, atetraalkoxytitanate, and mixtures thereof. The reaction mixture may alsoinclude a solvent. The solvent may be one or more of benzene, toluene,or one or more xylenes.

The concentration of the one or more lactams may be from about 0.075 Mto 10 M. The mole ratio of the one or more lactams to the one or morecarbonyl compounds may be from about 1:10 to 5:1. The catalyst may bepresent in an amount of less than about 30 mole percent relative to theamount of carbonyl compound. The lactam may be caprolactam orlaurolactam.

Another method for forming the multi-functional carbonyl compoundinvolves combining one or more lactams of general structure

wherein n, R^(a), R^(b), R^(c), and R^(d) are as defined above with oneor more carbonyl compounds of general structure

wherein D, B, Y, and m are as defined above; and a basic catalyst toprovide a reaction mixture; reacting the reaction mixture at atemperature less than about 20° C. for a sufficient time to produce themulti-functional carbonyl compound; and recovering the multi-functionalcarbonyl compound from the reaction mixture. The temperature may lessthan about 15° C. The reaction may be conducted in a solvent. The basecatalyst may be methoxide.

DETAILED DESCRIPTION OF THE INVENTION

An improved class of HALS compounds has now been discovered thatprovides substantially similar or superior UV light protection over alonger period of time compared to conventional HALS compounds. The HALScompounds of the present invention are based on the reaction of a lactamwith the carbonyl group of a carbonyl compound. The HALS compounds ofthe present invention include compounds where the functional componentof the HALS compound, a piperidin-4-ol or 4 aminopiperidine group, isanchored to the terminus of a hydrocarbon chain by an esterfunctionality or an amide functionality and wherein the other end of thehydrocarbon chain terminates with an amide linkage that is not a HALSfunctionality. These may be referred to as “ester/amide HALS compounds”and “amide/amide HALS compounds.” Alternatively, both ends of thehydrocarbon chain can terminate with the piperidin-4-ol or 4aminopiperidine group. In this embodiment, the HALS molecule is anchoredto one terminus of the hydrocarbon chain by an ester functionality andto the other terminus by a urethane functionality. These may be referredto as “ester/urethane HALS compounds.” Furthermore, the HALS moleculemay be anchored to one terminus of the hydrocarbon chain by an amidefunctionality and to the other terminus by a urea functionality. Thesemay be referred to as “amide/urea HALS compounds.” In yet another seriesof compounds, the piperidin-4-ol or 4 aminopiperidine group is bonded byan ester linkage to one terminus of the hydrocarbon chain and by anoxamate linkage at the other terminus of the hydrocarbon chain toprovide “ester/oxamate HALS compounds,” or the piperidin-4-ol or 4aminopiperidine group is bonded by an amide linkage to one terminus ofthe hydrocarbon chain and by an oxamide linkage at the other terminus ofthe hydrocarbon chain to provide “amide/oxamide HALS compounds.”

Monomeric HALS Compounds of the Invention

These HALS compounds are represented by the general formula (I)

RZ—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—A  (I)

wherein n is an integer from 1 to 15, preferably 4 to 11; m is either 0or 1; R^(a), R^(b), R^(c), and R^(d), are each a hydrogen or ahydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p), wherein R¹ and R^(f) areeach a hydrogen or hydrocarbyl group and p is zero or an integer from 1to 20 or CO—C₆H₄—, and the substitution pattern on the phenylene group,i.e., —₆H₄—, may be an ortho, meta, or para substitution pattern, inaddition one or more of the hydrogens of the phenylene group may besubstituted by a hydrocarbyl group or other functional group commonlyfound in organic molecules; Z is —O— or NG, wherein G is H, C₁-C₁₂ alkylor the radical R; wherein the radical R represents:

wherein R¹ is hydrogen, C₁-C₁₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy,C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy,C₃-C₆ alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted orsubstituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphaticC₁-C₈ acyl; R² is hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal Rmoieties, which together with the carbon to which they are attached,form a C₅-C₁₀ cycloalkyl; and A is either ZR or a hydrocarbyl group.

The term “hydrocarbyl,” as used herein, is a monovalent hydrocarbongroup in which the valency is derived by extraction of a hydrogen from acarbon. Hydrocarbyl includes, for example, aliphatics (straight andbranched chain), cycloaliphatics, aromatics and mixed character groups(e.g., aralkyl and alkaryl). Hydrocarbyl also includes groups withinternal unsaturation and activated unsaturation. More specifically,hydrocarbyl includes, but is not limited to, alkyl, cycloalkyl, aryl,aralkyl, alkaryl, alkenyl, cycloalkenyl, and alkynyl, typically havingfrom about 1 to 24 carbon atoms, preferably having from about 1 to 12carbon atoms. A hydrocarbyl may contain one or more carbonyl groups(which is/are included in the carbon count) and/or a heteroatom orheteroatoms (such as at least one oxygen, nitrogen, sulfur, or silicon)in the chain or ring. In addition, a hydrocarbyl may have one or more ofthe hydrogens of the hydrocarbon group replaced by a functional groupcommonly found in organic molecules. The phrase “functional groupcommonly found in organic molecules” means non-hydrocarbyl groups thatare typically found in organic molecules including, but not limited to,halides, cyano groups, amino groups, thiol groups, carboxylate groups,hydroxyl groups, sulfonate groups, nitroso groups, nitro groups, and thelike.

The term “hydrocarbylene” in the context of the present invention is adivalent hydrocarbon group in which both valencies derive by abstractionof hydrogens from carbon atoms. Included within the definition ofhydrocarbylene are the same groups as indicated above for hydrocarbyland functional hydrocarbyl with, of course, the extra valency (forexample, alkylene, alkenylene, arylene, etc.).

In a preferred embodiment of the invention, R¹ is H, C₁-C₄ alkyl, C₁-C₁₈alkoxy, C₅-C₁₂ cycloalkoxy, O, or OH; R₂ is H, or C₁-C₄ alkyl; R³, R⁴,R⁵, and R⁶ are H or C₁-C₄ alkyl; R^(a), R^(b), R^(c), and R^(d), areeach a hydrogen, aromatic, or C₁-C₄ alkyl; and n is from about 2 to 10.In a more preferred embodiment, R represents the2,2,6,6-tetramethylpiperidine radical (i.e., R³, R⁴, R⁵, R⁶ are methyland R² is hydrogen) or 1,2,2,6,6-pentamethylpiperidine radical (i.e.,R², R³, R⁴, R⁵, and R⁶ are methyl); R^(a), R^(b), R^(c), and R^(d) areeach a hydrogen; Z is —O—; m is 0 or 1; and n is 4 to 10.

Synthesis of Monomeric HALS Compounds

The HALS compounds of the formula (I) are typically prepared by thereaction of a multi-functional carbonyl compound with a 4-piperidin-olor a 4-aminopiperidine moiety. The multi-functional carbonyl compoundhas the general structure:

DO—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—B

wherein n is an integer from 1 to 15, preferably 4 to 11; m is either 0or 1; R^(a), R^(b), R^(c) and R^(d), are each a hydrogen or ahydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f)are each a hydrogen or hydrocarbyl group, and p is zero or an integerfrom about 1 to 20 or CO—C₆H₄—, and the substitution pattern on thephenylene group, i.e., —₆H₄—, is an ortho, meta, or para substitutionpattern, in addition one or more of the hydrogens of the phenylene groupmay be substituted by a hydrocarbyl group or a functional group commonlyfound in organic molecules; D is a hydrocarbyl group; and B is either ODor D; and reacting the carbonyl compound with a 1-substitutedpiperidin-4-ol or 4-aminopiperidine of general structure:

wherein Z is OH or NHG, wherein G is H or C₁-C₁₂ alkyl or the radical R(wherein R is defined above); and R¹ is hydrogen, C₁-C₁₈ alkyl, O, OH,CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂hydroxycycloalkoxy, C₃-C₆ alkenyl, C₁-C₁₈ alkynyl, C₇-C₉ phenylalkyl,unsubstituted or substituted on the phenyl with 1, 2 or 3 C₁-C₄ alkyls,or an aliphatic C₁-C₈ acyl; R² is hydrogen, C₁-C₈ alkyl, or benzyl; R³,R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, ortwo geminal R moieties, which together with the carbon to which they areattached, to form a C₅-C₁₀ cycloalkyl.

The reaction between the multi-functional carbonyl compound and the4-piperidin-ol or 4-aminopiperidine moiety is conducted for a sufficienttime for the compound of formula (I) to be formed. The phrase “conductedfor a sufficient time for the compound of [a given formula] to beformed” means that after the reactants are combined they are allowed toreact for sufficient time to produce a detectable amount of the desiredcompound, i.e., the compound of a given formula. By “detectable amount ”of a compound is meant an amount of the compound that can be detected byany means readily available to those of ordinary skill in the art. Meansfor detecting the formation of a compound in a reaction mixture include,but are not limited to, thin layer chromatography (TLC), highperformance liquid chromatography (HPLC), gas chromatography (GC),column chromatography, nuclear magnetic resonance spectroscopy (NMR),infra-red (IR) spectroscopy, ultra-violet (UV) or visible (VIS)spectroscopy, and wet-chemical analysis, for example. The length of timefor the desired compound to be produced is dependent on a number ofvariables and, thus, cannot be generalized. For example, the reactiontime is dependent on the temperature, the pressure, the specificreactants (i.e., the multi-functional carbonyl compound and the1-substituted piperidin-4-ol or 4-aminopiperidine), and the solvent andcatalyst, if present. Acceptable parameters that produce the desiredproduct, however, may be readily determined by those of ordinary skillin the art without undue experimentation.

The reaction may be carried out in the absence of a solvent or in thepresence of a solvent. When the reaction is carried out in the absenceof a solvent either the multi-functional carbonyl compound or the4-piperidin-ol or 4-aminopiperidine may be present in an excess andemployed as the reaction medium. Alternatively, the multi-functionalcarbonyl compound and 4-piperidin-ol or 4-aminopiperidine can be presentin a stoichiometric amount. The multi-functional carbonyl compound and4-piperidin-ol or 4-aminopiperidine may be present in a melt.Preferably, the reaction is carried out in an organic solvent. Anysolvent compatible with the reagents may be used. Preferred solvents foruse in the method of the invention include, but are not limited to,hydrocarbon solvents such as a saturated alkanes; benzene; toluene;xylenes; halogenated hydrocarbons; ethers such as ethyl ether; cyclicethers such as tetrahydrofuran and dioxane; amides such asdimethylformamide; sulfoxides such as dimethylsulfoxide; ketones such as2-butanone or methyl isobutyl ketone; and the like; or combinationsthereof. The more preferred solvents include toluene, benzene, andxylenes.

When the reaction is carried out in a solvent the concentration of themulti-functional carbonyl in the organic solvent is generally from about0.025 M to 2.5 M, preferably from about 0.125 M to 2 M, and morepreferably from about 0.25 M to 1.35 M. The molar ratio of the1-substituted piperidin-4-ol or 4-aminopiperidine to themulti-functional carbonyl compound is between about 20:1 and 1:5,preferably between about 10:1 and 1:3, and more preferably between about5:1 and 1:5.

The reaction of the multi-functional carbonyl compound and4-piperidin-ol or 4-aminopiperidine produces an alcohol of structureDOH. Preferably, the alcohol is removed from the reaction mixture as itis formed to help drive the reaction to completion. The alcohol may beremoved by any means available to those of ordinary skill in the artsuch as distillation and or azeotropic distillation.

Preferably, the reaction is conducted in the presence of a catalyst. Theoptional catalyst may be a basic or an acidic catalyst. The phrase “basecatalyst” means any compound that can abstract a proton. Base catalystssuitable for the invention include, but are not limited to, alkoxideions; hydroxide ion; amide ion; and amines such as triethylamine, DBU(1,8-diazabicyclo[5.4.0]undec-7-ene), or DBN(1,5-diazabicyclo[4.3.0]non-5-ene). When an amine is used as the base,it is preferred that the amine is a tertiary amine.

The phrase “acid catalyst” means any inorganic or organic acid with atleast one acidic proton or a Lewis acid. The organic acids include anyorganic compound that contains at least one acidic functional group,including one or more of RCO₂H, RSO₃H, RSO₂H, RSH, ROH, RPO₃H, RPO₂H,wherein R is a hydrocarbyl group. Preferred protic acids include HCl,HBr, HI, HNO₃, HNO₂, H₂S, H₂SO₄, H₃PO₄, H₂CO₃, acetic acid, formic acid,propionic acid, butanoic acid, benzoic acid, phthalic acid, oxalic acid,malonic acid, succinic acid, glutaric acid, adipic acid, methanesulfonicacid, and p-toluenesulfonic acid, or mixtures thereof. Lewis acidssuitable for the method of the invention include, but are not limitedto, aluminum halides, alkylaluminum halides, boron halides, dialkyl tinoxides and derivatives thereof, tin halides, titanium halides, leadhalides, zinc halides, iron halides, gallium halides, arsenic halide,copper halides, cadmium halides, mercury halides, antimony halides, andthe like. Preferred Lewis acids include aluminum trichloride, aluminumtribromide, 1,3,-diacetoxy-1,1,3,3-tetrabutyldistannoxane,trimethylaluminum, boron trifluoride, boron trichloride, zincdichloride, titanium tetrachloride, titanium (IV) isopropoxide, tindichloride, tin tetrachloride, a tetraalkoxytitanate or a mixturethereof.

The acid or base catalyst may also be a solid supported catalyst such asamberlyst catalysts.

The catalyst is typically added in an amount of less than about 30 molepercent based on the molar quantity of the multi-functional carbonylcompound, preferably less than about 20 mole percent based on the molarquantity of the multi-functional carbonyl compound, more preferably lessthan about 10 mole percent based on the molar quantity of themulti-functional carbonyl compound, and most preferably less than about5 mole percent by weight based on the weight of the multi-functionalcarbonyl compound.

The preferred base catalyst for use in the method of the invention ismethoxide ion. The preferred acid catalyst is a Lewis acid. Thepreferred Lewis acid is 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane.

Preferably, the reaction is allowed to proceed for a time that is lessthan about 20 hours and more preferably less than about 10 hours.Typically, the reaction temperature is from about room temperature to150° C., for example, up to the boiling point of the solvent. Typically,the reactions are run at atmospheric pressure. Representative reactionconditions for forming the compound of formula (I) are provided in theexamples.

After the compound of formula (I) is formed, it is recovered from thereaction mixture by any means available to those of ordinary skill inthe art. Methods for recovering compounds from a reaction mixtureinclude, but are not limited to, chromatography, recrystallization,distillation, extraction, and the like. More than one method may be usedto recover a compound from the reaction mixture.

In a preferred embodiment, the substituted 4-piperidin-4-ol is1,2,2,6,6-pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-piperidinoland the multi-functional carbonyl compound is methyl6-(methoxycarbonylamino)hexanoate, butyl6-(butoxycarbonylamino)undecanoate, methyl6-(butoxycarbonylamino)undecanoate, butyl6-(methoxycarbonylamino)undecanoate, or methyl6-(methoxycarbonylamino)undecanoate.

The multi-functional carbonyl compounds can be prepared by any methodavailable to those of ordinary skill in the art. In one embodiment, themulti-functional carbonyl compound is prepared by reacting a lactam witha carbonyl compound. For example, the multi-functional carbonyl compoundcan be prepared by the base catalyzed reaction of a lactam and acarbonyl compound according to the method disclosed in U.S. Pat. No.5,300,678, the contents of which are expressly incorporated herein byreference thereto.

Any lactam may be used according to the method of the invention.Preferably the size of the lactam ring is from about 4 to 13 atoms. Morepreferably the lactam is caprolactam or laurolactam.

The carbonyl compound must include at least one reactive carbonyl group.“Reactive carbonyl group” means any carbonyl group that is attached to agood leaving group and, thus, is activated towards nucleophilic acylsubstitution. The reactive carbonyl group may be, for example, an esteror acid chloride. Preferably the carbonyl compound is an ester. Morepreferred carbonyl compounds include dialkyl carbonates, dialkyloxalates, dialkyl diesters, or alkyl esters. The general structure ofthe carbonyl compound is

wherein m is either 0 or 1, Q is a good leaving group, such as chlorideor OD, wherein D is a hydrocarbyl group, preferably methyl, and B is Qor a hydrocarbyl group and Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) andR^(f) are each a hydrogen or hydrocarbyl group and p is zero or aninteger from about 1 to 20 or CO—C₆H₄—, and the substitution pattern onthe phenylene group, i.e., —₆H₄—, may be an ortho, meta, or parasubstitution pattern, in addition one or more of the hydrogens of thephenylene group may be substituted by a hydrocarbyl group or otherfunctional group commonly found in organic molecules.

When the carbonyl compound is a dialkyl carbonate, the resultingmulti-functional carbonyl compound is a hydrocarbon chain thatterminates on one end with an ester functionality and the other end witha urethane functionality. When the carbonyl compound is a dialkyloxalate, the resulting multi-functional carbonyl compound is ahydrocarbon chain that terminates on one end with an ester functionalityand the other end with an oxamate functionality. When the carbonylcompound is a dialkyl ester, the resulting multi-functional carbonylcompound is a hydrocarbon chain that includes an amide linkage andterminates on each end with an ester functionality. When the carbonylcompound is an alkyl ester, the resulting multi-functional carbonylcompound is a hydrocarbon chain that terminates on one end with an esterfunctionality and the other end with an amide functionality.

The reaction of the lactam with the carbonyl compound can be conductedin a solvent or in the absence of a solvent. When the reaction isconducted in the absence of a solvent, excess carbonyl compound may beemployed as the reaction medium and, thus, the carbonyl compound may bepresent in an excess compared to the lactam. The lactam, however, mayalso be present in an excess and employed as the reaction medium.Alternatively, the lactam and carbonyl compound can be present in astoichiometric amount. The lactam and carbonyl compound may be presentin a melt. When the reaction is conducted in the absence of a solvent,the excess carbonyl compound or lactam may be recovered by, for example,distillation and reused. An advantage of not using a solvent is that theproblems associated with disposal of waste solvents are avoided.

In another embodiment one or more different lactams are reacted with oneor more different carbonyl compounds. For example, two lactam moleculescan be reacted with 1 molecule of carbonyl compound.

Solvents suitable for the method of the invention include, but are notlimited to, hydrocarbon solvents such as a saturated alkane; benzene;toluene; xylenes; halogenated hydrocarbons; ethers such as ethyl ether;cyclic ethers such as tetrahydrofuran and dioxane; amides such asdimethylformamide; sulfoxides such as dimethylsulfoxide; ketones such as2-butanone or methyl isobutyl ketone; alcohols; and the like; ormixtures thereof. When the reaction is carried out in a solvent theconcentration of the lactam in the solvent is from about 0.025 M to 10M, preferably from about 0.375 M to 6 M, and more preferably from about0.25 M to 4 M. The mole ratio of lactam to carbonyl compound istypically from about 1:10 to 5:1, preferably from about 1:5 to 2:1, andmore preferably from about 1:2.5 to 1.5:1.

The reaction is allowed to proceed for a sufficient time to form adetectable amount of the multi-functional carbonyl compound. In generalthe reaction time is less than about 12 hours. Typically, the reactiontemperature is from about room temperature to 150° C., for example, upto the boiling point of the solvent, when a solvent is used. Thereaction is typically conducted at room temperature.

The present invention also provides an improved method for preparing themulti-functional carbonyl compound. According to the method of theinvention the lactam and a carbonyl compound are reacted in the presenceof an acid catalyst, preferably a Lewis acid catalyst.

Any Lewis acid catalyst can be used according to the method of theinvention. For example, any of the above-mentioned Lewis acid catalystsmay be used. Preferably the Lewis acid catalyst is titanium (IV)isopropoxide. Lewis acids are a preferred catalyst since they can beeasily removed from the reaction mixture. For example, many Lewis acids,such as tetraorganotitanates, can be readily hydrolyzed with astoichometric amount of water, leading to a highly insoluble titaniumdioxide that can easily be removed from the reaction mixture byfiltration. Other Lewis acids, such as, for example, boron trifluorideetherate, are sufficiently volatile that they can easily be removed fromthe reaction mixture by distillation. Thus, using a Lewis acid canadvantageously avoid having to extract the reaction mixture with anaqueous solvent to remove the catalyst. By avoiding an extraction stepto remove the catalyst, the method of the invention generates lessaqueous waste that ultimately has to be disposed of.

In another improved method of the invention, the lactam and carbonylcompound are allowed to react with an alkoxide anion as a basiccatalyst, preferably methoxide anion. The reaction, however, isconducted at a temperature of less than about 20° C., preferably lessthan about 19° C., and more preferably less than about 15° C. The lactamand carbonyl compound are allowed to react for less than about 5 hours,preferably less than about 2 hours, and more preferably less than about1 hour. Conducting the reaction at a low temperature is preferred sincetemperatures can be kept below the flash point of many reagents and,thus, such low temperature reactions can be significantly safer. Forexample, dimethyl carbonate (which is a common carbonyl compound for usein the method of the invention) has a flash point of 19° C. By runningthe reaction at a temperature below 19° C., i.e., below the flash point,the method is significantly safer than prior art methods that requirehigher temperatures.

When the multi-functional carbonyl compound is formed, it can berecovered from the reaction mixture before it is reacted with the1-substituted piperidin-4-ol or 4-aminopiperidine to form the HALS ofthe invention. The multi-functional carbonyl compound may be recoveredby any means available to those of ordinary skill in the art.Optionally, the multi-functional carbonyl compound is not recovered fromthe reaction mixture and instead the 1-substituted piperidin-4-ol or4-aminopiperidine is added to the reaction mixture after a detectableamount of the multi-functional carbonyl compound is formed. The1-substituted piperidin-4-ol or 4-aminopiperidine and themulti-functional carbonyl compound can then react to form the HALS ofthe invention.

In a preferred method, the compound of formula (I) is prepared byreacting the lactam, carbonyl compound, and 1-substituted piperidin-4-olor 4-aminopiperidine in a single step. The lactam, the carbonylcompound, and the 1-substituted piperidin-4-ol or 4-aminopiperidine arecombined and allowed to react at the same time, rather than reacting thelactam and carbonyl compound to form the multi-functional carbonylcompound in a first step and then, in a subsequent step, reacting themulti-functional carbonyl compound with the 1-substituted piperidin-4-olor 4-aminopiperidine. The lactam, the carbonyl compound, and the1-substituted piperidin-4-ol or 4-aminopiperidine are combined in areaction vessel and allowed to react for sufficient time to form adetectable amount of the HALS of formula (I).

The ratio of lactam to carbonyl compound in this embodiment of themethod is from about 2:1 to 1:4, preferably from about 1:1 to 1:2; andthe ratio of lactam to 1-substituted piperidin-4-ol or 4-aminopiperidineis from about 1:1 to 1:6, preferably from about 1:2 to 1:4.

The single step reaction can be conducted in a solvent or in the absenceof a solvent. When a solvent is used, any solvent that is compatiblewith the reagents may be used. Representative solvents include, but arenot limited to, those solvents described above for the reaction of a1-substituted piperidin-4-ol or 4-aminopiperidine with amulti-functional carbonyl compound. Preferably, the reaction in thisembodiment is carried out in the presence of a solvent. When a solventis employed, the concentration of lactam is typically from about 0.025 Mto 10 M, preferably from about 0.325 M to 6 M, and more preferably fromabout 0.75 M to 4 M.

Preferably, the reaction is carried out in the presence of a catalyst.The same catalysts may be used as were used in the reaction of a1-substituted piperidin-4-ol or 4-aminopiperidine with amulti-functional carbonyl compound. The catalyst is typically present inan amount of less than about 30 mole percent, preferably less than about20 mole percent, and more preferably less than about 10 mole percent,and most preferably less than 5 mole percent, relative to the amount ofcarbonyl compound.

Preferably, the carbonyl compound is an ester, i.e., Q=OD, so that thereaction produces an alcohol of structure HOD. Preferably, the alcoholis removed from the reaction mixture as it is formed to drive thereaction to completion. The alcohol may be removed by any meansavailable to those of ordinary skill in the art, such as distillationand/or azeotropic distillation.

Preferably, the reaction time is less than about 20 hours and morepreferably less than about 10 hours. Typically, the reaction temperatureis between about room temperature and 250° C. Typically, the reactionsare run at atmospheric pressure. Representative reaction conditions forforming the HALS of formula (I) by the single step process are providedin the examples. When the HALS of formula (I) is formed it may berecovered from the reaction mixture by any means available to those ofordinary skill in the art.

Oligomeric HALS Compounds of the Invention

The invention also includes oligomeric HALS having the general formula(II)

TE—F_(i)E—F′_(j)E′—F′_(k)E′—F′_(l)S  (II)

wherein i, j, k, and l are integers from about 0 to 300, preferablyabout 0 to 200, and more preferably 0 to about 100. The sum of i, j, k,and l is greater than 2, preferably, the sum of i, j, k, and l isgreater than about 3 and more preferably is greater than about 6.Preferably at least two of i, j, k, and l or more, or (III)

TM—F_(i)—M—F′_(j)—M  (III)

wherein i and j are integers from about 0 to 300, preferably about 0 to200, and more preferably 0 to about 100. The sum of i and j is greaterthan 2. Preferably, the sum of i and j is greater than about 3, morepreferably greater than about 6. Preferably at least two of i, j, k, andl are equal to or greater than 1.

In formula (II) E and E′ are a piperidin-4-ol or 4-aminopiperidinemoiety and F and F′ are each a multi-functional carbonyl compound. T canbe F, F′, or hydrogen and S can be E, E′, or hydrogen.

E—F includes:

E—F′ includes:

E′—F includes:

and E′—F′ includes:

In formula (III), M is a diamino or a dihydroxy group that contains the4-aminopiperidine group, R, as defined above. By “diamino or a dihydroxygroup” is meant a group derived from a compound that contains at leasttwo hydroxy groups, at least two amino groups, or at least one aminogroup and one hydroxy group. The amino group can be either a primary orsecondary amino group.

M—F includes:

M—F′ includes:

In the oligomeric HALS of formula (III) the diamino or dihydroxy groupthat contains the 4-aminopiperidine group, i.e., M, is bonded to themulti-functional carbonyl compound by the hydroxy or amino group.

Formulas II and III may be a block copolymer or a random copolymer,i.e., the units E—F, E—F′, E′—F, and E′—F′ or M—F and M-F′ aredistributed randomly throughout the polymer chain. In the aboveoligomeric HALS of structure (II) or (III) S is a hydrogen, or a unitderived from a piperidin-4-ol or a 4-aminopiperidine moiety and has thestructure

and T is a hydrogen or a unit derived from a multi-functional carbonylcompound and has the structure

wherein D is a hydrocarbyl group.

In the oligomeric HALS of formula (II) and (III) n is an integer from 1to 15, preferably 4 to 11, m is either 0 or 1, s is 0 or an integer fromabout 1 to 10; R^(a), R^(b), R^(c), and R^(d), are each a hydrogen or ahydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f)are each a hydrogen or hydrocarbyl group and p is zero or an integerfrom about 1 to 20 or CO—C₆H₄—, wherein the substitution pattern on thephenylene group is an ortho, meta, or para substitution pattern, and oneor more of the hydrogens of the phenylene group may be substituted by ahydrocarbyl group or a functional group commonly found in organicmolecules; Z is —O— or NG, wherein G is H or C₁-C₁₂ alkyl; R² ishydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ are each ahydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal R moieties,which together with the carbon to which they are attached, form a C₅-C₁₀cycloalkyl; and when s is greater than 0, P is NH or O; and when s is 0,P═O or O—L—O, where L is a hydrocarbylene.

As noted above, in the HALS of formula (II), E, E′ and S are unitsderived from a piperidin-4-ol or a 4-aminopiperidine moiety and F, F′and T are units derived from a multi-functional carbonyl compound and inthe HALS of formula (III) F and F′ are derived from a multi-functionalcarbonyl compound and M is as defined above. In the HALS of formula (II)it is preferably that the mole percent of the units derived from themulti-functional carbonyl compound is greater than the mole percent ofthe units derived from a piperidin-4-ol or a 4-aminopiperidine moiety.In the HALS of formula (III) it is preferably that the mole percent ofthe units derived from the multi-functional carbonyl compound is greaterthan the mole percent of the diamino or dihydroxy group that containsthe 4-aminopiperidine group, i.e., M. This is advantageous since theyare less expensive.

Preferably, in the oligomeric HALS of formula (II), R² is H, or C₁-C₄alkyl; R³, R⁴, R⁵, and R⁶ are each H or C₁-C₄ alkyl; R^(a), R^(b),R^(c), and R^(d), are each a hydrogen, aromatic, or C₁-C₄ alkyl; n isfrom about 4 to 11; and s is from about 2 to 5. In a more preferredembodiment, R² is a hydrogen; R³, R⁴, R⁵, and R⁶ are each methyl; R^(a),R^(b), R^(c), and R^(d), are each a hydrogen, Z is O, n is between 4 and11, and s is 2, m is 0 and P is O.

In another embodiment, R² is hydrogen, R³, R⁴, R⁵ and R⁶ are methyl,R^(a), R^(b), R^(c) and R^(d) are each hydrogen, Z is O, n is from 4 to11 and s is 0.

Preferably, in the oligomeric HALS of formula (III), M isN,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine (BPIP) orN-(2,2,6,6-tetramethylpiperidinol) diethanolamine and n is from about 4to 11.

Advantageously, the number average molecular weight of the oligomericHALS compound of formula (II) and (III) is typically from about 400 to20,000, preferably, from about 1,000 to 15,000, and more preferably fromabout 2,000 to 9,000.

Synthesis of Oligomeric HALS Compounds

The present invention also relates to a method of forming oligomericHALS of formula (II) and formula (III). Oligomeric HALS of formula (II)are prepared by reacting a multi-functional carbonyl compound of generalstructure

 DO—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—OD  (IV)

wherein n is an integer from about 1 to 15, preferably 4 to 11, m iseither 0 or 1; R^(a), R^(b), R^(c), and R^(d), are each a hydrogen or ahydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f)are each a hydrogen or hydrocarbyl group and p is zero or an integerfrom about 1 to 20 or CO—C₆H₄—, wherein the substitution pattern on thephenylene group may be an ortho, meta, or para substitution pattern, andone or more of the hydrogens of the phenylene group may be substitutedby a hydrocarbyl group or a functional group commonly found in organicmolecules; and D is a hydrocarbyl group, with a 1-substitutedpiperidin-4-ol or 4-aminopiperidine of general structure:

wherein Z is OH or or NHG, wherein G is H or C₁-C₁₂ alkyl; R¹ is—(CH₂)_(s)—OH, —(CH₂)_(s)—NH₂, C₁-C₁₈ hydroxyalkoxy or C₅-C₁₂hydroxycycloalkoxy; wherein s is an integer from about 1 to 10,preferably 2 to 8; R² represents hydrogen, C₁-C₈ alkyl, or benzyl; R³,R⁴, R⁵, and R⁶ are each a hydrogen, C₁-C₈ alkyl, benzyl or phenethyl, ortwo geminal R moieties, which together with the carbon to which they areattached, form a C₅-C₁₀ cycloalkyl.

Oligomeric HALS of formula (III) are prepared by reacting amulti-functional carbonyl compound of general structure (IV) with adiamino or a dihydroxy compound that contains the 4-aminopiperidinegroup. Preferably, the diamino or dihydroxy compound includesN,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine (BPIP) orN-(2,2,6,6-tetramethylpiperidinol) diethanolamine.

The multi-functional carbonyl compounds are prepared by any methodavailable to those of ordinary skill in the art. Preferably, themulti-functional carbonyl compounds are prepared by the method of theinvention wherein a carbonyl compound is reacted with a lactam in thepresence of a Lewis acid or wherein a carbonyl compound is reacted witha lactam and an alkoxide at a low temperature, i.e., less than 20° C.The carbonyl compound, however, must have two reactive carbonyl groupsor a single carbonyl group that is activated with two leaving groups(for example, phosgene or a dialkyl carbonate). Preferably, the leavinggroup is an ester. Preferred carbonyl compound include dialkylcarbonates, dialkyl oxalates, and dialkyl esters.

The reaction can be carried out in the absence of a solvent or in thepresence of an organic solvent. When the reaction is carried out in theabsence of a solvent, either the multi-functional carbonyl compound orthe 1-substituted piperidin-4-ol or 4-aminopiperidine (for compound(II)) or the diamino or dihydroxy compound that contains the4-aminopiperidine group (for compound (III)) may be present in an excessand employed as the reaction medium. Alternatively, the multi-functionalcarbonyl compound and the 1-substituted piperidin-4-ol or4-aminopiperidine or the diamino or a dihydroxy compound that containsthe 4-aminopiperidine group can be present in stoichiometric amounts.The reaction can also be conducted in a melt.

Preferably, the reaction is carried out in an organic solvent. Anysolvent compatible with the reagents may be used. Preferred solvents foruse in the method of the invention include, but are not limited to,hydrocarbon solvents such as a saturated alkanes; benzene; toluene;xylenes; halogenated hydrocarbons; ethers such as ethyl ether; cyclicethers such as tetrahydrofuran and dioxane; amides such asdimethylformamide; sulfoxides such as dimethylsulfoxide; ketones such as2-butanone or methyl isobutyl ketone; and the like; or a mixturethereof. The more preferred solvents include toluene, benzene, andxylenes, or a mixture thereof.

The concentration of the multi-functional carbonyl compound in theorganic solvent is generally present in an amount of from about 0.025 Mto 2.5 M, preferably from about 0.125 M to 0.2 M, and more preferablyfrom about 0.25 M to 1.35 M. The molar ratio of the multi-functionalcarbonyl compound to the 1-substituted piperidin-4-ol or4-aminopiperidine, used to prepare the oligomeric HALS of formula (II),or to the diamino or dihydroxy compound that contains the4-aminopiperidine group, used to prepare the oligomeric HALS of formula(III), is from about 5:1 to 1:5, preferably from about 2:1 to 1:2, andmore preferably from about 1.2:1 to 1:1.2.

In a preferred embodiment of the method of making the oligomeric HALS offormula (II), the substituted piperidin-4-ol or 4-aminopiperidineincludes N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol. In apreferred embodiment of the method of making the oligomeric HALS offormula (III), the diamino or a dihydroxy compound that contains the4-aminopiperidine group 4-aminopiperidine includes BPIP orN-(2,2,6,6-tetramethyl piperidinol) diethanolamine or a mixture thereof.

Optionally, but preferably the reaction is conducted in the presence ofa catalyst. The catalyst may be a basic catalyst or an acid catalyst.Preferably, the base catalyst is methoxide ion. Preferably the acidcatalyst includes a Lewis acid. The preferred Lewis acid includes1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane.

The catalyst is typically added in an amount of less than about 30 molepercent by weight based on the weight of the multi-functional carbonylcompound, preferably less than about 20 mole percent by weight based onthe weight of the multi-functional carbonyl compound, more preferablyless than about 10 mole percent by weight based on the weight of themulti-functional carbonyl compound, and most preferably less than about5 mole percent by weight based on the weight of the multi-functionalcarbonyl compound.

The reaction of the multi-functional carbonyl compound and the1-substituted piperidin-4-ol or 4-aminopiperidine, used to prepare theoligomeric HALS of formula (II), or the diamino or dihydroxy compoundthat contains the 4-aminopiperidine group, used to prepare theoligomeric HALS of formula (III), is conducted for sufficient time toform a detectable amount of the oligomeric HALS of formula (II) or(III). The reaction time temperature and pressure may readily bedetermined by one of ordinary skill in the art without undueexperimentation. Typically, the reaction time is less than about 20hours, preferably less than about 15 hours, and more preferably lessthan about 10 hours. Typically, the reaction temperature is from aboutroom temperature to about 150° C., for example, up to the boiling pointof the solvent. Preferably, the reaction is carried out at atmosphericpressure. Representative reaction conditions for forming the compound offormula (II) or (III) are provided in the examples.

After the oligomeric HALS of formula (II) or (III) are formed, they arerecovered from the reaction mixture by any means available to those ofordinary skill in the art.

In a preferred method, the oligomeric HALS of formula (II) and (III) areformed by reacting a lactam, a carbonyl compound of general structure

wherein m is either 0 or 1, Q is a good leaving group, such as chlorideor OD, wherein D is a hydrocarbyl group, preferably methyl, and B is Qor a hydrocarbyl group and Y is CO—(CR^(e)R^(f))_(p), wherein R^(e) andR^(f) are each a hydrogen or hydrocarbyl group and p is zero or aninteger from about 1 to 20 or CO—C₆H₄—, and the substitution pattern onthe phenylene group may be an ortho, meta, or para substitution pattern,in addition one or more of the hydrogens of the phenylene group may besubstituted by a hydrocarbyl group or other functional group commonlyfound in organic molecules, and a 1-substituted piperidin-4-ol or4-aminopiperidine, in the case of oligomeric HALS of formula (II), or adiamino or a dihydroxy compound, in the case of oligomeric HALS offormula (III), in a single step. The lactam, carbonyl compound, and a1-substituted piperidin-4-ol or 4-aminopiperidine or a diamino or adihydroxy compound that contains the 4-aminopiperidine group arecombined in a reaction vessel and allowed to react for sufficient timeto form a detectable amount of the compound of formula (II) or (III).The ratio of lactam to carbonyl compound is from about 2:1 to 1:4,preferably from about 1:1 to 1:2 and the ratio of lactam to1-substituted piperidin-4-ol or 4-aminopiperidine or diamino or adihydroxy compound is from about 2:1 to 1:2, preferably about 1:1.

The single step reaction may be conducted in a solvent or in the absenceof a solvent. Preferably, the reaction is conducted in the presence of asolvent. When a solvent is used any solvent that is compatible with thereagents may be used. Representative solvents include, but are notlimited to, those solvents described above for the reaction of a1-substituted piperidin-4-ol or 4-aminopiperidine with amulti-functional carbonyl compound. When a solvent is employed, theconcentration of the lactam is typically from about 0.075 M to 10 M,preferably from about 0.375 M to 6 M, and more preferably from about0.75 M to 4 M.

Optionally, but preferably, the reaction is carried out in the presenceof a catalyst. The same catalysts may also be used as were used in thereaction of a 1-substituted piperidin-4-ol or 4-aminopiperidine with amulti-functional carbonyl compound. The catalyst is typically present inan amount of less than about 30 mole percent, preferably less than about20 mole percent, more preferably less than about 10 mole percent, andmost preferably less than 5 mole percent relative to the amount ofcarbonyl compound.

In general the reaction time is less than about 20 hours, preferablyless than about 15 hours, and more preferably less than about 10 hours.Typically, the reaction temperature is from about room temperature to250° C. Preferably, the reaction is carried out at atmospheric pressure.Representative reaction conditions for forming the oligomeric HALS in asingle step according to the method of the invention can readily bedetermined by one of ordinary skill in the art, but guidance is alsoprovided in the examples.

When the oligomeric HALS of formula (II) or (III) is formed it may berecovered from the reaction mixture by any means available to those ofordinary skill in the art.

Polymeric Articles Including HALS and Manufacture of the Same

The HALS of the present invention, i.e., HALS of formula (I), (II), or(III) may be provided as neat compounds or may be provided in the formof a concentrate including from about 15 to 98 percent by weight, andpreferably from about 20 to 95 percent by weight, preferably from about25 to 90 percent by weight, and more preferably from about 40 to 70percent of at least one of the HALS compounds of formula (I), (II), or(III) and a polymeric resin.

The HALS compounds of the present invention impart superiorweatherability and yellowing resistance to polymers. In addition, theHALS compounds of the present invention typically exhibit lowvolatility. Thus, the present invention also provides polymeric articlesstabilized by including an effective amount of the newly discovered HALScompounds to inhibit at least one of photo- or thermal degradation andmethods of making the polymeric articles. Any suitable polymercompatible with a HALS composition of the invention may be combined withone or more HALS of the invention to form a polymeric article protectedfrom UV light. The polymeric article includes at least one polymericmaterial and a sufficient amount of at least one HALS of formula (I),(II), or (III) to inhibit at least one of photo- or thermal degradation.Typically, the polymeric article is stabilized by blending from about0.01 percent to 10 percent by weight, preferably from about 0.03 percentto 1 percent by weight, and more preferably from about 0.05 percent to0.5 percent by weight of at least one HALS of formula (I), (II), or(III) with a polymeric material used to form the article. The articlemay be an extruded article, a molded article, a tape, a film, a fiber,or a coating, for example.

The method of making the polymeric articles includes blending apolymeric material with from about 0.01 percent to 10 percent by weight,preferably from about 0.03 percent to 1 percent by weight, and morepreferably from about 0.05 percent to 0.5 percent by weight at least oneHALS compounds of the present invention to form a stabilized polymericcomposition, and forming an article from the polymeric composition. Thepolymeric article may be formed by extrusion, sheet extrusion, injectionmolding, blow molding, injection blow molding, rotational orroto-molding, calendering, thermoforming, compression molding, vacuummolding, pressure molding, reaction injection molding, solvent casting,fiber spinning, and other similar techniques available to those ofordinary skill in the art. The HALS of the invention may be added to thepolymeric material by any means known in the art, and one of ordinaryskill in the art may readily envision a variety of such ways to combineone or more HALS compounds and one or more polymeric materials to formpolymeric articles according to the invention.

A variety of other conventional additives, individually or incombination, may also be added to the polymeric material. Examples ofsuch additives include, but are not limited to one or more of thefollowing classes:

a. Antioxidants

(i) Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol; nonylphenols which are liner orbranched in the side chains such as 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1-methylundec-1-yl)phenol,2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol,2,4-dimethyl-6-(1-methyltridec-1-yl)phenol, CYANOX® 1790, CYANOX® 2246,and CYANOXO® 425 Antioxidants, commercially available from CYTECINDUSTRIES of West Paterson, N.J., IRGANOX® 1010 Antioxidant andIRGANOX® 1076 Antioxidant, commercially available from of CIBASPECIALTIES of Hawthorne, N.Y., and mixtures thereof;

(ii) Alkylthiomethylphenols, such as2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol, and mixtures thereof;

(iii) Hydroquinones and alkylated hydroquinones, such as2,6-di-tert-butyl-4-methoxyhenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

(iv) Tocopherols, such as α-tocopherol (vitamin E), β-tocopherol,γ-tocopherol, δ-tocopherol, and mixtures thereof;

(v) Hydroxylated thiodiphenyl ethers, such as2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide,and mixtures thereof;

(vi) Alkylidenebisphenols, such as2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxylbenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, andmixtures thereof;

(vii) O-, N- and S-benzyl compounds, such as3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, and mixturesthereof;

(viii) Hydroxybenzylate malonates, such asdioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,and mixtures thereof;

(ix) Aromatic hydroxybenzyl compounds, such as1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, and mixturesthereof;

(x) Triazine compounds, such as2,4-bis(octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, and mixturesthereof;

(xi) Benzylphosphonates, such asdimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and mixtures thereof;

(xii) Acylaminophenols, such as 4-hydroxylauranilide,4-hydroxystearanilide, and octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate, and mixtures thereof;

(xiii) Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid;β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid;β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid;3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydricalcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and mixturesthereof;

(xiv) Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,such asN,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, andmixtures thereof;

(xv) Ascorbic acid (Vitamin C) or salt or ester thereof;

(xvi) Aminic antioxidants, such as N,N′-diisopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfonamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine such asp,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminophenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, -allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl)hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol,and mixtures thereof;

b. Conventional UV-absorbers and Light Stabilizers

(i) 2-(2′-Hydroxyaryl)benzotriazoles, such as2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole or2-(2H-benzotriazol-2-yl)-4-tert-octyl-phenol known as CYASORB® UV-5411Light Stabilizer, commercially available from CYTEC INDUSTRIES of WestPaterson, N.J.,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)-benzotriazole,2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole, amixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol], the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]benzotriazolewith polyethylene glycol 300, [R—CH₂CH—COO(CH₂)₃]₂— whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl phenyl, TINUVIN® 900Light Stabilizer, commercially available from CIBA SPECIALTIES, andmixtures thereof;

(ii) 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octoxy CYASORB® UV-531 Light Stabilizer, commercially available fromCYTEC INDUSTRIES), 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy compounds, and mixturesthereof;

(iii) Esters of substituted and unsubstituted benzoic acids or salicylicacid compounds, such as 4-tert-butyl-phenyl salicylate, phenylsalicylate, octylphenyl salicylate, dibenzoyl resorcinol,bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol,2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, and2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate,and mixtures thereof;

(iv) Acrylates or alkoxycinnamates, such as ethylα-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate,methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate,N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, and mixtures thereof;

(v) Nickel compounds including nickel (II) complexes of amines andthio-bis-phenols, such as nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], including the 1:1 or1:2 complex, with or without additional ligands, such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of monoalkyl esters including themethyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes including 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands, and mixtures thereof;

(vi) Sterically hindered amines, as well as the N compounds thereof(e.g., N-alkyl, N-hydroxy, N-alkoxy and N-acyl), such asbis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethylpiperidin-4-yl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione,3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione,a mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]),N-(2,2,6,6-tetramethyl piperidine-4-yl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane,oxo-piperanzinyl-triazines or so called PIP-T HALS, e.g., GOODRITE®3034, 3150 and 3159 commercially available form BF Goodrich Chemical Co.of Akron, Ohio and similar materials disclosed in U.S. Pat. No.5,071,981, photobondable HALS such as SANDUVOR® PR-31 AND PR-32commercially available from Clariant Corp. of Charlotte N.C., andsimilar materials disclosed in GB-A-2269819, the reaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decaneand epichlorohydrin. Examples of the tetramethylpiperidine derived HALSinclude CYASORB® UV-3346 Light Stabilizer, commercially available fromCYTEC INDUSTRIES, SANDUVOR® 3055 HALS, SANDUVOR® 3056 HALS, andSANDUVOR® 3058 HALS, commercially available from SANDOZ Corporation ofCharlotte, N.C., CHIMASORB® 944 Stabilizer, TINUVIN® 622 Stabilizer, andTINUVIN® 144 Stabilizer, each commercially available from CIBASPECIALTIES, and mixtures thereof. See also generally U.S. Pat. Nos.5,106,891, 4,740,542, 4,619,956, 4,426,471, 4,426,472, 4,356,307,4,344,876, 4,314,933; GB-A-2269819, EP-A-309400, EP-A-309401,EP-A-309402 and EP-A-0434608, each of which is incorporated herein byreference in their entirety;

(vii) Oxamides, oxanilides, benzoxazinones, benzoxazoles, or triazines,such as 2,2′-(1,4-methylene)bis[4H-3,1-benzoxazin-4-one] (CYASORB®UV-3638 Light Stabilizer, commercially available from CYTEC INDUSTRIES),4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide,2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o-and p-methoxydisubstituted oxanilides and mixtures of o- and p-ethoxydisubstitutoctyloxyphenyl-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, andCYAGARD® UV-1164L Light Stabilizer, commercially available from CYTECINDUSTRIES, and mixtures thereof;

(c) Metal deactivators, such as N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide, and mixturesthereof;

(d) Phosphites and phosphonites including peroxide decomposers, such asalkyl phosphites, aryl phosphites, and aralkyl phosphites, such astriphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkylphosphites, tris(nonylphenyl) phosphite, trilauryl phosphite,trioctadecyl phosphite, distearyl pentaerythritol diphosphite ULTRANOX®618 Antioxidant, bis-(2,4-di-tert-butylphenyl)pentaerythritoldiphosphiteULTRANOX® 626 Antioxidant, commercially available from GE SpecialtyChemicals of Parkersburg, W. Va.,tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, bis(isodecyloxy)pentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butyl)phenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite,tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite, and mixturesthereof;

(e) Hydroxylamines, such as N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecyl-hydroxylamine,-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow fatty amines, and mixtures thereof;

(f) Nitrones, such as N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone,N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrones derived fromN,N-dialkylhydroxylamines prepared from hydrogenated tallow fattyamines, and mixtures thereof;

(g) Thiosynergists, such as dilauryl thiodipropionate and distearylthiodipropionate, and mixtures thereof;

(h) Peroxide scavengers such as esters of β-thiodipropionic acid, forexample the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate, and mixtures thereof;

(i) Polyamide stabilizers, such as copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese, andmixtures thereof;

(j) Basic co-stabilizers, such as melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea compounds, hydrazine compounds,amines, polyamides, polyurethanes, alkali metal salts and alkaline earthmetal salts of higher fatty acids, for example calcium stearate, zincstearate, magnesium behenate, magnesium stearate, sodium ricinoleate andpotassium palmitate, antimony pyrocatecholate, tin pyrocatecholate, andmixtures thereof;

(k) Nucleating agents including inorganic substances, such as talc andmetal oxides (e.g., titanium oxide or magnesium oxide), and phosphates,carbonates and sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and salts thereof, forexample 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid,sodium succinate and sodium benzoate; polymeric compounds such as ioniccopolymers (“ionomers”), and mixtures thereof;

(l) Fillers and reinforcing agents, such as calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite, wood flour andflours or fibers from other natural products, and synthetic fibers, andmixtures thereof;

(m) Benzofuranones and indolinones, such as those disclosed in U.S. Pat.Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, and 5,252,643, andDE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 and EP-A-0591102;3-[4-(2-acetoxy-ethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)-phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,and mixtures thereof;

(n) Sulfur containing antioxidants, such as organic sulfides anddisulfides and include distearyl thiodipropionate CYANOX® STDPAntioxidant, commercially available from CYTEC INDUSTRIES,pentaerythritol tetrakis(beta-laurylthiopropionate) SEENOX® 412 SAntioxidant, commercially available from Witco Chemical Corporation ofBrooklyn, N.Y., and mixtures thereof. A person skilled in the art iswell aware, for example, that any one or more of these additives may becombined, such as in CYANOX® 2777 Antioxidant, commercially availablefrom CYTEC INDUSTRIES, which combines a phenolic antioxidant and aphosphite antioxidant. The composition may contain quenchers such asCYASORB® UV-1084 Light Stabilizer, CYASORB® UV-531 Light Stabilizer,each commercially available from CYTEC INDUSTRIES.

(o) Other additives, such as acid scavengers, antistatic agents, blowingagents, catalysts, clarifying agents, emulsifiers, fillers,flameproofing agents, fluorescent whitening agents, infrared absorbers,levelling assistants, lubricants, metal deactivators, mold releaseagents, nucleating agents, optical brighteners, pigments, plasticizers,rheological additives, and mixtures thereof.

The total amount of additives may be present in an amount up to about 10percent, preferably from about 0.1 percent to about 5 percent by weight,and more preferably from about 0.2 percent to 3 percent by weight, basedon the weight of the polymer.

The light-stabilized polymeric article may be formed from a polymericmaterial by incorporating the presently claimed compounds into polymericmaterials, either chemically or physically. Non-limiting examples ofpolymeric materials that may be so stabilized are polyolefins;polyesters; polyethers; polyketones; polyamides; natural and syntheticrubbers; polyurethanes; polystyrenes; high-impact polystyrenes;polyacrylates; polymethacrylates; polyacetals; polyacrylonitriles;polybutadienes; polystyrenes; ABS; SAN (styrene acrylonitrile); ASA(acrylate styrene acrylonitrile); cellulosic acetate butyrate;cellulosic polymers; polyimides; polyamideimides; polyetherimides;polyphenylsulfides; PPO; polysulfones; polyethersulfones;polyvinylchlorides; polycarbonates; polyketones; aliphatic polyketones;thermoplastic TPO's; aminoresin crosslinked polyacrylates andpolyesters; polyisocyanate crosslinked polyesters and polyacrylates;phenol/formaldehyde, urea/formaldehyde, and melamine/formaldehyderesins; drying and non-drying alkyd resins; alkyd resins; polyesterresins; acrylate resins cross-linked with melamine resins, urea resins,isocyanates, isocyanurates, carbamates, and epoxy resins; cross-linkedepoxy resins derived from aliphatic, cycloaliphatic, heterocyclic andaromatic glycidyl compounds which are cross-linked with anhydrides oramines; polysiloxanes; Michael addition polymers of amines or blockedamines with activated unsaturated and methylene compounds, ketimineswith activated unsaturated and methylene compounds, polyketimines incombination with unsaturated acrylic polyacetoacetate resins, andpolyketimines in combination with unsaturated acrylic resins; radiationcurable compositions; epoxymelamine resins; organic dyes; cosmeticproducts; cellulose-based paper formulations; photographic film paper;ink; and blends thereof.

The degradable polymer may be any polymer requiring stabilization, andincludes homopolymers and copolymers of various monomers. It may be anaddition polymer, a condensation polymer, a graft polymer, athermosetting polymer, a photopolymer, a polymer blend or athermoplastic polymer. It may be in the form of a fiber, a polymer filmsuch as polypropylene films, a thin film such a solvent based coating, awater-based coating, a stoving lacquer, a powder coating, a gel coat,and the like, or it may be in the form of a molded article. Examples ofdegradable polymers which can be stabilized include, but are not limitedto:

1. Homo- and copolymers of monoolefins and diolefins including, but notlimited to, ethylene, propylene, isobutylene, butene, methylpentene,hexene, heptene, octene, isoprene, butadiene, hexadiene,dicyclopentadiene, ethylidene, and cycloolefins such as cyclopentene andnorbornene; for example, polyethylenes (which optionally can becross-linked) such as high density polyethylene (HDPE), high density andhigh molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), branched low density polyethylene (BLDPE) orpolypropylene (PP) or polymers of ethylene propylene diene monomer(EPDM); and blends thereof.

2. Copolymers of one or more monoolefins and/or diolefins with carbonmonoxide and/or with other vinyl monomers, including acrylic andmethacrylic acid, acrylates and methacrylates, acrylamides,acrylonitriles, styrenes, vinyl acetate (such as ethylene/vinyl acetatecopolymers (EVA)), vinyl halides, vinylidene halides, maleic anhydride,and allyl monomers such as allyl alcohol, allyl amine, allyl glycidylether and compounds thereof; and blends thereof.

3. Hydrocarbon resins (such as C₅-C₉) including hydrogenatedmodifications thereof, and mixtures of polyalkylenes and starch ; andblends thereof.

4. Homo- and copolymers of styrenes such as styrene, p-methylstyrene andα-methylstyrene such as polystyrene, polyalphamethylstyrene, high impactpolystyrene (HIPS); and blends thereof.

5. Copolymers of one or more styrenes with other vinyl monomers such asolefins and diolefins (e.g., ethylene, isoprene and/or butadiene),acrylic and methacrylic acid, acrylates and methacrylates, acrylamides,acrylonitriles, vinyl acetate (such as ethylene/vinyl acetatecopolymers), vinyl halides, vinylidene halides, maleic anhydride andallyl compounds such as allyl alcohol, allyl amine, allyl glycidylether; and blends thereof.

6. Graft copolymers of styrenes on polybutadienes, polybutadiene/styrenecopolymers and polybutadiene/acrylonitrile copolymers; styrene (orα-methylstyrene) and acrylonitrile (or methacrylonitrile) onpolybutadiene; styrene and maleic anhydride on polybutadiene; styrene,acrylonitrile and maleic anhydride or maleimide on polybutadiene;acrylonitrile/styrene/acrylonitrile polymers (ASA) styrene andacrylonitrile on ethylene/propylene/diene copolymers; styrene andacrylonitrile on polyalkyl acrylates or methacrylates; and styrene andacrylonitrile on acrylate/butadiene (ABS) copolymers; and blendsthereof.

7. Halogen-containing polymers such as poly vinyl chloride (PVC),chlorinated polyethylene (CPE), or polychloroprene; chlorinated rubbers;chlorinated and brominated isobutylene/isoprene copolymers; chlorinatedor sulfochlorinated polyethylene; copolymers of ethylene and chlorinatedethylene; epichlorohydrin polymers and copolymers; and polymers andcopolymers of halogen-containing vinyl compounds such as vinyl chloride,vinylidene chloride, vinyl fluoride and/or vinylidene fluoride, othervinyl monomers or other polyvinyl halides; and blends thereof.

8. Homo- and copolymers derived from α,β-unsaturated acids and compoundsthereof such as acrylic acid, methacrylic acid, acrylates,methacrylates, acrylamides and acrylonitriles; and blends thereof.

9. Copolymers of the monomers mentioned in (5) above with otherunsaturated monomers such as olefins and diolefins (e.g., butadiene),styrenes, vinyl halides, maleic anhydride and allyl monomer such asallyl alcohol, allyl amine, allyl glycidyl ether; and blends thereof.

10. Homo- and copolymers derived from unsaturated alcohols and amines orthe acyl compounds or acetals thereof, such as vinyl alcohol (includingpolyvinyl alcohol cross-linked polyvinyl alcohol), vinyl acetate, vinylstearate, vinyl benzoate, vinyl maleate, vinyl butyral, allyl alcohol,allyl amine, allyl glycidyl ether, allyl phthalate and allyl melamine;as well as copolymers of such monomers with other ethylenic unsaturatedmonomers mentioned above; and blends thereof.

11. Homo- and copolymers of cyclic ethers such as alkylene glycols andalkylene oxides, as well as copolymers with bisglycidyl ethers; andblends thereof.

12. Polyacetals such as polyoxymethylene (POM) and thosepolyoxymethylenes which contain ethylene oxide as a comonomer; andpolyoxymethylenes modified with thermoplastic polyurethanes, acrylatesand/or MBS; and blends thereof.

13. Polyphenylene oxides (PPO) and sulfides; and blends thereof.

14. Polyurethanes (PUR) derived from hydroxy-functional components suchas polyhydric alcohols, polyethers, polyesters, polyacrylics and/orpolybutadienes on the one hand, and aliphatic and/or aromaticisocyanates on the other, as well as precursors thereof includingisocyanate cross-linked polymers; and blends thereof.

15. Polyamides (PA) and copolyamides derived from diamines, dicarboxylicacids and/or aminocarboxylic acids or the corresponding lactams, such asNYLON® plastics, e.g., polyamide 4, polyamide 6, polyamide 6/6,polyamide 6/10, polyamide 6/9, polyamide 6/12, polyamide 4/6, polyamide12/12, polyamide 11 and polyamide 12; aromatic polyamides starting fromm-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without anelastomer as a modifier, for example, poly-2,4,4-trimethylhexamethyleneterephthalamide or poly-m-phenylene isophthalamide; block copolymers ofthe aforementioned polyamides with polyolefins, olefin copolymer,ionomers, chemically bonded or grafted elastomers, or polyethers such aspolyepoxides, polyethylene glycol, polypropylene glycol orpolytetramethylene glycol; and polyamides condensed during processing(RIM polyamide systems); and blends thereof.

16. Polyureas, polyimides, polyamide-imides, polyetherimides,polyesterimides, polyhydantoins and polybenzimidazoles; and blendsthereof.

17. Polyesters derived from dicarboxylic acids, diols and/orhydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate (PET), polybutylene terephthalate (PBT),polyethylene terephthalate, glycol modified (PETG), polyethyleneterephthalate modified with 1,4-cyclohexanedimethanol(PCTG),poly-1,4-dimethylcyclohexane terepthalate andpolyhydroxybenzoates, as well as block copolyether esters derived fromhydroxyl-terminated ethers; and also polyesters modified withpolycarbonate or MBS; PEN, PTT; and blends thereof.

18. Polycarbonates (PC) and polyester carbonates such as resins arepolycarbonates based on dihydric phenols such as2,2-bis-(4-hydroxyphenyl)propane (bisphenol A);2,4-bis(4-hydroxyphenyl)-2-methylbutane;1,1-bis-(4-hydroxyphenyl)-cyclohexane;2,2-bis-(3-chloro-4-hydroxyphenyl)propane; 4,4′-sulfonyldiphenol; and1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; and blendsthereof. Also preferred are polycarbonate copolymers incorporating twoor more phenols, branched polycarbonates wherein a polyfunctionalaromatic compound is reacted with a dihydric phenol(s) and carbonateprecursor, and polymer blends of which polycarbonate comprises asignificant portion of the blend (i.e., more than 20%, preferably morethan 50%). Preferred resins for both layers are polycarbonates based onbisphenol A.

U.S. Pat. No. 5,288,788 also describes polycarbonates and polyestercarbonates, especially aromatic polycarbonates, for example those basedon 2,2-bis(4-hydroxyphenyl)propane or1,1-bis(4-hydroxyphenyl)cyclohexane. Mixtures (polyblends) of suchpolymers with one another or with other polymers, for example withpolyolefins, polyacrylates, polydienes or other elastomers in the formof impact strength modifiers can also be stabilized with the HALScompounds of the invention.

Among those compounds, preference is given to the polycarbonates,polyesters, polyamides, polyacetals, polyphenylene oxides andpolyphenylene sulfides, but especially to the polycarbonates. Thosecompounds are to be understood as being especially those polymers theconstitutional repeating unit of which corresponds to the formula:

wherein A is a divalent phenolic radical. Suitable examples of A aregiven in U.S. Pat. No. 4,960,863 and DE-A-3 922,496 whose contents areincorporated herein by reference thereto. “A” can be derived, forexample, from hydroquinone, resorcinol, dihydroxybiphenylene orbisphenols in the broadest sense of the term, such asbis(hydroxyphenyl)alkanes, cycloalkanes, sulfides, ethers, ketones,sulfones, sulfoxides, α,α′-bis(hydroxyphenyl)-diisopropylbenzenes, forexample the compounds 2,2-bis(4-hydroxyphenyl)propane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-propane,2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,1,1-bis(4-hydroxypehnyl)cyclohexane, or from the compounds of theformula:

19. Polysulfones, polyether sulfones and polyether ketones.

20. Cross-linked polymers derived from aldehydes condensation resinssuch as phenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins; and blends thereof.

21. Drying and non-drying alkyd resins; and blends thereof.

22. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof; and blends thereof.

23. Cross-linkable acrylic resins derived from substituted acrylatessuch as epoxy acrylates, hydroxy acrylates, isocyanato acrylates,urethane acrylates or polyester acrylates; and blends thereof.

24. Alkyd resins, polyester resins and acrylate resins cross-linked withmelamine resins, urea resins, isocyanates, isocyanurates, carbamates orepoxy resins; and blends thereof.

25. Cross-linked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic and/or aromatic glycidyl compounds such as bisphenol A andbisphenol F, which are cross-linked with customary hardeners such asanhydrides or amines; and blends thereof.

26. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous compounds thereof, including cellulose acetates,cellulose propionates and cellulose butyrates, nitrocellulose, or thecellulose ethers such as methyl cellulose, as well as rosins and theircompounds; and blends thereof.

27. Polysiloxanes; and blends thereof.

28. Michael addition polymers of amines or blocked amines (e.g.,ketimines) with activated unsaturated and/or methylene compounds such asacrylates and methacrylates, maleates and acetoacetates; and blendsthereof.

29. Mixtures or blends of any of the above, such as PP/EPDM,polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS,PC/ASA, PC/PBT, PVC/CPE, PVC/acrylate, POM/thermoplastic PUR,PC/thermoplastic polyurethane, POM/acrylate, POM/MBS, PPO/HIPS,PPO/PA6.6 and copolymers, PA/HDPE, PP/HDPE, PP/LDPE, LDPE/HDPE,LDPE/EVA, LDPE/EAA, PA/PP, PA/PPO, PBT/PC/ABS, PBT/PET/PC and the like.

30. Naturally occurring and synthetic organic materials which may bemixtures of compounds, including mineral oils, animal and vegetablefats, oils and waxes, or oils, fats or waxes based on synthetic esters(e.g., phthalates, adipates, phosphates or trimellitates) and alsomixtures of synthetic esters with mineral oils in any ratio.

31. Aqueous emulsions of natural or synthetic rubber such as naturallatex or latexes of carboxylated styrene/butadiene copolymers; andblends thereof.

32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins includingurethane acrylates, polyether acrylates, vinyl or acryl copolymers withpendant unsaturated groups and acrylated melamines; and blends thereof.

33. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer; andblends thereof.

34. Epoxymelamine resins such as light-stable epoxy resins cross-linkedby an epoxy functional coetherified high solids melamine resin. Theaminoresin-cross-linked polymer may be an aminoresin-cross-linkedthermoset acrylic or an aminoresin-cross-linked thermoset polyester. Thesuitable aminoresins include alkylated and unalkylatedmelamine-formaldehyde resins, guanamine-formaldehyde resins,urea-formaldehyde resins, glycouril formaldehyde resins, and the like;and blends thereof.

35. Organic dyes such as azo dyes (diazo, triazo, and polyazo),anthraquinones, benzodifuranones, polycyclic aromatic carbonyl dyes,indigoid dyes, polymethines, styryl dyes, di- and triaryl carboniumdyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitrosodyes, stilbene dyes, formazan dyes, quinacridones, carbazoles, andperylene tetracarboxylic diimides; and blends thereof.

36. Cosmetic products, such as skin lotions, collagen creams, sunscreen,facial make up, etc., comprising synthetic materials such asantioxidants, preservatives, lipids, solvents surfactants, colorants,antiperspirants, skin conditioners, moisturizers etc.; as well asnatural products such as collagen, proteins, mink oil, olive oil,coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum,aloe, etc; and blends thereof.

37. Cellulose-based paper formulations for use, e.g., in newsprint,cardboard, posters, packaging, labels, stationery, book and magazinepaper, bond typing paper, multi-purpose and office paper, computerpaper, xerographic paper, laser and ink-jet printer paper, offset paper,currency paper, etc., and combinations thereof.

38. Photographic film paper.

39. Ink.

The term “copolymer,” as used herein, is a polymer of two or moredifferent monomers. Preferably, the light-stabilized polymeric materialis formed from a polyolefin homopolymer or copolymer, and morepreferably a homopolymer or copolymer of polyethylene or polypropylene.

The novel HALS of the present invention can also be employed inmultilayer systems. In such systems, a polymer composition having fromabout 0.1 to 20 percent by weight and preferably having a relativelyhigh content of the novel HALS of the invention, for example, from about5 to 15 percent by weight, is applied in a thin film (typically betweenabout 5 to 500 μm and preferably from about 10 to 100 μm thick) to ashaped article made from a polymer containing little or no ultravioletstabilizers. Such composition may be applied at the same time as theshaping of the base structure, for example by coextrusion.Alternatively, application can also be made to the ready-formed basestructure, for example by lamination with a film or by coating with asolution. The outer layer or layers of the finished article have thefunction of a UV filter, which protects the interior of the article fromUV light. The outer layer preferably contains about 0.1 to 20 percent,preferably about 1 to 15 percent and more preferably about 2 to 10percent by weight of the outer layer composition, of at least one of theHALS of the present invention.

British Patent Appn. No. 2,290,745 describes a number of methods thathave been developed to concentrate UV absorbers near or at the surfaceof polymeric materials. These include surface impregnation (see U.S.Pat. Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937,026) and coating aplastic article with solutions containing thermoplastic resins and UVabsorbers (see U.S. Pat. Nos. 4,668,588 and 4,353,965). Both techniques,however, suffer from drawbacks such as requiring additional processingsteps (i.e., applying, drying or curing), and encounter difficultiesassociated with the handling of large processed articles. An additionaldrawback, particularly relevant to polycarbonate sheet production, isthe detrimental effect such post addition treatment would have on thesurface of the polymeric substrate.

As described in the U.S. Pat. No. 5,445,872, application of surfacelayers via coextrusion takes place in a known manner with knowncoextrusion equipment as taught in U.S. Pat. Nos. 3,487,505 and3,557,265, which is a preferred way to incorporate HALS compounds ontothe surface of a polymeric article according to the present invention.Coextrusion is a well recognized method of producing laminatedthermoplastic materials by simultaneously extruding various numbers oflayers which form a single composite material. U.S. Pat. No. 4,540,623describes coextruded materials of at least forty layers. Other methodsknown to those of ordinary skill in the art produce as few as two orthree different layers.

In one embodiment, the invention relates to thermoplastic articlescoated with a thermoplastic layer about 0.1 to 10 mil (0.00254 mm to0.254 mm) thick, preferable about 0.1 to 5 mil (0.00254 mm to 0.127 mm)thick, in which the layer contains between about 0.1% to 20% by weightof one or more of the HALS of the invention. Preferred concentrationsare from about 2% to 15% by weight; most preferred are concentrationsfrom about 5% to 10% by weight.

The HALS of the instant invention may be incorporated into thethermoplastics of the surface layer by standard methods, such as drymixing the additives with a granular resin prior to extruding. The HALSlayer may be applied to one or more sides of a thermoplastic articleaccording to the present invention.

Laminated thermoplastic articles corresponding to the present inventionwhich contain additional layers such as a water resistant layer, asfound in U.S. Pat. No. 4,992,322, are also within the scope of thepresent invention.

The core layer and the coating layer may be of the same thermoplasticresin or different. Examples of thermoplastic resins includethermoplastic polyesters, polyester carbonates, polyphenylene oxide,polyvinyl chloride, polypropylene, polypropylene, polyethylene,polyacrylates, polymethacrylates and copolymers and blends such asstyrene and acrylonitrile on polybutadiene and styrene with maleicanhydride; and blends thereof.

The polymers stabilized in this way are notable for high weatheringresistance, especially for high resistance to UV light. This enablesthem to substantially retain their mechanical properties and their colorand gloss for a long time even when used in harsh environments.

Coating Stabilizers Including HALS Compounds and Preparation of the Same

In another embodiment of the present invention, novel mixturescomprising at least one HALS of the invention can be used as stabilizersfor coatings, for example for paints. Of particular interest arecoatings and paints for the automobile industry. “Coating” means a freeflowing composition that can be applied to the surface of an article ina thin film that then hardens to form a substantially solid surface onthe article. Typically, the coating provides an interface between thearticle and the environment.

Such novel coating compositions comprise from about 0.01 to 20 percent,preferably from about 0.01 to 10 percent and more preferably from about0.02 to 5 percent by weight of one or more of the HALS of the presentinvention.

The coating may be applied to the surface of the article in one or morethan one layer to provide a multilayered system. In multilayer systems,the concentration of the novel HALS compounds in the outer layer can berelatively high, for example from about 0.01 to 20 percent, preferablyfrom about 0.01 to 10 percent, and more preferably from about 0.02 to 5percent by weight.

The use of the novel stabilizer in coatings is accompanied by theadditional advantage that it inhibits or prevents delamination, i.e.,the flaking-off of the coating from the substrate. This advantage isparticularly important in the case of metallic substrates, includingmultilayer systems on metallic substrates, which have such flakingtendencies.

The coatings typically include a binder that suspends pigments and otheradditives in the coating and allows attachment of the coating to thesubstrate.

The binder can in principle be any binder which is customary inindustry, for example those described in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim,1991, which is incorporated herein by reference. In general, it is afilm-forming binder based on a thermoplastic or thermosetting resin,predominantly on a thermosetting resin. Examples thereof are alkyd,acrylic, polyester, phenolic, melamine, epoxy, and polyurethane resins,and mixtures thereof.

Such binders can be a cold-curable or hot-curable binder. Further, insome systems it may be advantageous to add a curing catalyst to suchsystems. Suitable catalysts which accelerate curing of the binder aredescribed, for example, in Ullmann's Encyclopedia of IndustrialChemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft, Weinheim, 1991,which is incorporated herein by reference.

Preferred binders include those which comprise a functional acrylateresin and a crosslinking agent.

A wide variety of binders may be employed in such coating systems.Examples of suitable coating compositions containing specific binders,include but are not limited to:

1. paints based on cold- or hot-cross-linkable alkyd, acrylate,polyester, epoxy or melamine resins, or mixtures of such resins, ifdesired with addition of a curing catalyst;

2. two-component polyurethane paints based on hydroxyl-containingacrylate, polyester or polyether resins and aliphatic or aromaticisocyanates, isocyanurates or polyisocyanates; or mixtures thereof;

3. one-component polyurethane paints based on blocked isocyanates,isocyanurates or polyisocyanates which are deblocked during baking;ormixtures thereof;

4. two-component paints based on (poly)ketimines and aliphatic oraromatic isocyanates, isocyanurates or polyisocyanates; or mixturesthereof;

5. two-component paints based on (poly)ketimines and an unsaturatedacrylate resin or a polyacetoacetate resin or a methacrylamidoglycolatemethyl ester; or mixtures thereof;

6. two-component paints based on carboxyl- or amino-containingpolyacrylates and polyepoxides; or mixtures thereof;

7. two-component paints based on acrylate resins containing anhydridegroups and on a polyhydroxy or polyamino component; or mixtures thereof;

8. two-component paints based on (poly)oxazolines and acrylate resinscontaining anhydride groups, or unsaturated acrylate resins, oraliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; ormixtures thereof;

9. two-component paints based on unsaturated polyacrylates andpolymalonates; or mixtures thereof;

10. thermoplastic polyacrylate paints based on thermoplastic acrylateresins or externally crosslinking acrylate resins in combination withetherified melamine resins; or mixtures thereof;

11. paint systems based on siloxane-modified or fluorine-modifiedacrylate resins or mixtures thereof;

In addition to the binder and novel HALS of the present invention, thecoating composition according to the invention may further comprise oneor more additional additives, such as an antioxidant or additionalultraviolet light absorber or stabilizer. Additional additives include,but are not limited to, those specifically listed above. The additionaladditive is employed in coating compositions in an amount of from about0.01 to 5 percent, preferably from about 0.02 to 2 percent by weight.

In addition, well known to those of ordinary skill in the art to besuitable for coating compositions the coating composition can alsocomprise further components including, but not limited to, solvents,pigments, dyes, plasticizers, stabilizers, thixotropic agents, dryingcatalysts and/or leveling agents, or combinations thereof. Examples ofpossible components are those described in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim1991, which is incorporated herein by reference.

Exemplary drying catalysts or curing catalysts are, for example,organometallic compounds, amines, amino-containing resins and/orphosphines. Examples of organometallic compounds are metal carboxylates,especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metalchelates, especially those of the metal Al, Ti or Zr, or organometalliccompounds such as organotin compounds, for example, and mixturesthereof.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, theoctoates of Co, Zn or Cu, the naphthenates of Mn and Co or thecorresponding linoleates, resinates or tallates, and mixtures thereof.

Examples of metal chelates are the aluminum, titanium, or zirconiumchelates of acetylacetone, ethyl acetylacetate, salicylaldehyde,salicylaldoxime, o-hydroxyacetophenone, or ethyl trifluoroacetylacetate,and the alkoxides of these metals, and mixtures thereof.

Examples of organotin compounds are dibutyltin oxide, dibutyltindilaurate or dibutyltin dioctoate, and mixtures thereof.

Examples of amines are, in particular, tertiary amines, for exampletributylamine, triethanolamine, N-methyldiethanolamine,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine ordiazabicyclooctane (triethylenediamine) and salts thereof, and mixturesthereof. Further examples are quaternary ammonium salts, for exampletrimethylbenzylammonium chloride. Amino-containing resins aresimultaneously a binder and a curing catalyst. Examples thereof areamino-containing acrylate copolymers.

The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

The novel coating compositions can also be radiation-curable coatingcompositions. In this case, the binder includes monomeric or oligomericcompounds containing ethylenically unsaturated bonds, which afterapplication are cured by actinic radiation, i.e., converted into acrosslinked, high molecular weight form. Where the system is UV-curable,it generally contains a photoinitiator as well. Corresponding systemsare described in the above-mentioned publication Ullmann's Encyclopediaof Industrial Chemistry, 5th Edition, Vol. A18, pages 451-453, which isincorporated herein by reference. In radiation-curable coatingcompositions, the novel stabilizers can also be employed with or withoutadditional UV light stabilizers, including sterically hindered amines.

The coating compositions according to the invention can be applied toany desired substrates, for example to metal, wood, plastic, or ceramicmaterials. They are preferably used as topcoats in the finishing ofautomobiles. If the topcoat comprises two layers, of which the lowerlayer is pigmented and the upper layer is not pigmented, the novelcoating composition can be used for either the upper or the lower layeror for both layers, but preferably for the upper layer.

The novel coating compositions can be applied to the substrates by anyconventional methods available to those or ordinary skill in the art,for example by brushing, spraying, pouring, dipping, or electrophoresis;see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition,Vol. A18, pp. 491-500, which is incorporated herein by reference.

Depending on the binder system, the coatings can be cured at roomtemperature or may require heating. The coatings are preferably cured ata temperature of from about 50° C. to 150° C., and in the case of powdercoatings, even at higher temperatures.

The coatings obtained in accordance with the invention generally haveexcellent resistance to the damaging effects of light, oxygen, and heat.In particular, the presently claimed coatings provide good lightstability and weathering resistance.

The invention therefore encompasses coatings, in particular a paint,which has been stabilized against the damaging effects of light, oxygen,and/or heat by a content of at least one of the HALS of the presentinvention incorporated into or onto an article. The paint may be apigmented mono-coat which includes a film-forming binder and an organicpigment or dye, an inorganic pigment, a metallic pigment, or a mixturethereof. The paint may also be a composition which comprises a primer inadhesion to a metal or plastic substrate; a pigmented base coat that isin adhesion to the primer, and which comprises a film-forming binder andan organic pigment or dye, an inorganic pigment, a metallic pigment, ora mixture thereof; and a clear top coat that is in adhesion to the basecoat, and which comprises a film-forming binder and optionally atransparent pigment. The paint is preferably a topcoat for automobiles.

The invention furthermore relates to a process for stabilizing a coatingbased on organic polymers against damage by light, oxygen, and/or heat,which comprises mixing with the coating composition a mixture comprisingone or more HALS of the present invention, as well as the use ofmixtures comprising the one or more HALS of the present invention incoating compositions as stabilizers against damage by light, oxygen,and/or heat.

The coating compositions can comprise an organic solvent or solventmixture in which the binder is soluble. The coating composition canotherwise be an aqueous solution or dispersion. The carrier can also bea mixture of organic solvent and water. The coating composition may be ahigh-solids paint or can be solvent-free (e.g., a powder coatingmaterial).

The pigments can be inorganic, organic or metallic pigments. The novelcoating compositions preferably contain no pigments and preferably areused in clearcoat compositions.

Likewise preferred is the use of the coating composition as a topcoatfor applications in the automobile industry, especially as a pigmentedor unpigmented topcoat of the paint finish. Its use for underlyingcoats, however, is also possible.

EXAMPLES

The following examples are merely illustrative of preferred embodimentsof the present invention and are not to be construed as limiting theinvention, the scope of which is defined by the appended claims.

Examples 1-9 Preparation of HALS Compounds Based on Multi-functionalCarbonyl Compounds

Eight HALS compounds of the general structure depicted below weresynthesized according to the invention.

Compound I (n=5, R=Hydrogen) Compound II (n=5, R=Methyl) Compound III(n=11, R=Hydrogen) Compound IV (n=11, R=Methyl)

wherein i, j, k, and 1 are integers and the sum of i, j, k, and 1 isgreater than 2.

Compound VII (Mn=Approximately 2,000) Compound VIII (Mn=Approximately8,800)

Compounds I and II were prepared from methyl 6-(methoxycarbonylamino)hexanoate (Compound A), compounds III and IV were prepared from butyl6-methyl 6-[(methoxyoxoacetyl)amino]-hexanoate (Compound C) and compoundVI was prepared from methyl 6-(octanoylamino)hexanoate (Compound D).Compounds VII and VIII were prepared from compound A andN-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-peridinol.

Compound A (n=5, R=Methyl) Compound B (n=11, R=Butyl)

Compound C

Compound D

N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol was prepared by thehydrolysis of TINUVIN 622 with aqueous sodium hydroxide/tetrahydrofuran,removal of the tetrahydrofuran under reduced pressure, extraction of theaqueous layer with chloroform, drying and filtering the chloroformlayer, and removal of the chloroform under reduced pressure. Therecovered N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol had amelting point of 179-183° C. (literature melting point 182° C., DE U.S.Pat. No. 2,352,658). The synthesis of Compounds A, B, C and D aredescribed below.

Synthesis of Compound A:

To a 300 mL 3-necked round bottom flask equipped with a mechanicalstirrer, a ground glass stopper and a condenser fitted with an argoninlet and outlet to a bubbler was charged 10 g (88 mmol) of caprolactam,10.5 g (117 mmol) of dimethylcarbonate, 5.23 g (96.8 mmol) of sodiummethoxide, and 100 mL of methanol. The mixture was heated at reflux for24 hours, then cooled to room temperature. 7.3 g (121 mmol) of glacialacetic acid was added and the methanol removed by rotary evaporation.The residue was dissolved in 100 mL of methylene chloride and theorganic layer extracted with water to remove unreacted caprolactam.Solvent removal by rotary evaporation, followed by further solventremoval in vacuo (<1 mm) at 95° C. gave 5.23 g (29%) of compound A as anearly colorless oil. The structure of compound A was established byNMR. ¹H NMR (CDCl₃): δ 4.63 (br s, 1H, NH); 3.68 (s, 3H, CH₃—OCO); 3.66(s, 3H, CH₃—OCO); 3.17 (br dt, 2H, —CH ₂—NH—); 2.31 (t, 2H, —CH₂COO);1.65-1.21 (in, 6H, CH₂(CH ₂)₃CH₂).

Synthesis of Compound B:

To a three-necked, 250 mL reaction flask equipped with a magneticstirrer, a reflux condenser, and a thermometer adapter, was charged13.96 g (0.070 mol) of laurolactam, 13.4 g (0.076 mol) of dibutylcarbonate, 4.16 g (0.077 mol) of sodium methoxide, and 130 g of butanol.The mixture was heated for 64 hours at 110° C. After cooling to roomtemperature, 4.9 g (0.10 mol) of glacial acetic acid in 30 g of butanolwas added and the mixture stirred for 5 min. The resulting mixture wasdiluted with 500 mL of methylene chloride, washed with water, and dried(MgSO₄). Filtration and rotary evaporation gave 19.6 g of a greasysolid. Flash chromatography on 200-400 mesh, 60 Å silica gel (0.5%methanol/methylene chloride) gave 7.2 g (25%) of the title compound as awhite semi-solid. The structure of compound B was established by NMR. ¹HNMR (CDCl₃): δ 4.61 (br s, 1H, NH); 4.05 (q, 4H, —CH₂CH ₂—OCO); 3.16 (brdt, 2H, —CH ₂—NH—); 2.28 (t, 2H, —CH₂COO); 1.65-1.21 (m, 26H, CH₂(CH₂)₉CH₂, (CH ₂)₂CH ₃), 1.93 (t, 6H, CH₃).

Synthesis of Compound C:

To a 100-mL round bottom flask equipped with a stir bar was charged 8.45g (75 mmol) of caprolactam, 8.85 g (75 mmol) of dimethyl oxalate, and0.16 g (3 mmol) of sodium methoxide. The mixture was immersed in a 50°C. oil bath and heated for 30 min, then cooled over an hour to 35° C.After stirring at this temperature for several hours, the mixture wascooled and allowed to stand overnight at room temperature. The mixturewas diluted with 125 mL of methylene chloride and washed with water,then washed with saturated sodium chloride solution. Drying overmolecular sieves, filtration, and removal of solvent under reducedpressure gave 12.5 g (72% yield) of a light yellow liquid whichcrystallized to a low melting solid on standing. The structure of thematerial was confirmed by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 7.18 (br s,1H, NH); 3.90 (s, 3H, CH₃—OCOCO); 3.67 (s, 3H, CH₃—OCCH₂); 3.35 (app q,2H, —CH ₂—NH—); 2.32 Ct, (2H, —CH₂COO); 1.70-1.30 (m, 6H, CH₂(CH₂)₃CH₂).

Synthesis of Compound D:

To a 100-mL round bottom flask equipped with a stir bar was charged 16.9g (150 mmol) of caprolactam, 23.7 g (150 mmol) of methyl caprylate and0.32 g (6 mmol) of sodium methoxide. The mixture was immersed in a185-195° C. oil bath and heated for 58 hours. After cooling to 75° C.and addition of 0.35 g (6 mmol) of acetic acid the flask was cooledfurther and residual methyl caprylate (17 g) removed by distillation at48-67° C./0.8 mm, followed by caprolactam (10 g) at 90-95° C./0.8 mm.The residue was diluted with methylene chloride, washed with water tofurther remove caprolactam, dried (MgSO₄), filtered, and evaporatedunder reduced pressure to give compound D (6.3 g, 38% yield based onunrecovered caprolactam) as a light brown wax. The structure of thematerial was confirmed by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.60 (br m,1H, NH); 3.62 (s, 3H, CH₃—OCO); 3.20 (app q, 2H,—CH ₂—NH—); 2.25 (t, 2H,—CH₂COO—); 2.16 (t, 2H, —CH ₂CONH—); 1.70-1.18 (m, 16H, CH₂(CH ₂)₃CH₂,CH₂(CH ₂)₅CH₃).

Synthesis of a Mixture of Compound E and F:

To a 50 mL thick-walled reaction vessel equipped with a magnetic stirbar and a Teflon screw cap was added 10.6 g(53.7 mmol) of laurolactam,9.83 g (56.4 mmol) of dibutyl carbonate, and 0.58 g (10.7 mmol) ofsodium methoxide. The mixture was immersed in a 120° C. oil bath andheated for 2 hours. After cooling to room temperature the mixture wasdiluted with 100 mL of methylene chloride and to it was added 0.67 g(11.2 mmol) of acetic acid. Filtration and solvent removal by rotaryevaporation, followed by further solvent removal in vacuo (<1 mm) at 95°C. gave the product as an off-white paste. ¹H NMR (CDCl₃) indicated thepresence of mainly two compounds, E and F, in an approximately 80:20mole ratio. Flash chromatography (3.5% methanol/methylene chloride) gavepure samples of the two components.

Compound E: ¹H NMR (CDCl₃): δ 4.61 (br s, 1H, NH) 4.05 (q, 4H, —CH₂CH₂—OCO); 3.16 (br dt, 2H, —CH ₂—NH—); 2.28 (t, 2H, —2H, —CH₂COO);1.65-1.21 (m, 26H, CH₂(CH ₂)₉CH₂, (CH ₂)₂CH ₃), 0.93 (t, 6H, CH ₃).

Compound F: ¹H NMR (CDCl₃): δ 5.50 (br t, 1H, —CH₂ NHCOCH₂); 4.65 (br s,1H —CH ₂ NHCOOCH₂ 4.05 (q, 4H, —CH₂CH ₂—OCO); 3.21 (dt 2H, —CH ₂NHCOCH₂—); 3.16 (br dt, 2H, —CH ₂ NHCOOCH₂); 2.28 (t, 2H, —CH₂COO); 2.15(t, 2H, —CH ₂CONH); 1.65-1.21 (M, 26H, CH₂(CH ₂)₉CH₂, (CH ₂)₂CH₃) 0.93(t, CH ₃).

The lower temperature reaction of these reactants gives little or nocompound F.

Synthesis of a Mixture of Compound G and H:

To a 50 mL thick-walled reaction vessel equipped with a magnetic stirbar and a Teflon screw cap as added 6.06 g (53.7 mmol) of caprolactam,9.83 g (56.4 mmol) of dibutyl carbonate, and 0.58 g (10.7 mmol) ofsodium methoxide. The mixture was immersed in a 129° C. oil bath andheated for 2 hours. After cooling to room temperature the mixture wasdiluted with 100 mL of methylene chloride and to it was added 0.67 g(11.2 mmol) of acetic acid. Filtration and solvent removal by rotaryevaporation, followed by further solvent removal in vacuo (<1 mm) at 95°C. gave the product as a yellow paste. ¹H NMR (CDCl₃) indicated thepresence of compounds G and H in an approximately 80:20 mole ratio.

The lower temperature reaction of these reactants gives little or nocompound H.

Synthesis of a Mixture of Compound I and J:

To a 25 thick-walled reaction vessel equipped with a magnetic stir barand a Teflon screw cap was added 2.26 g (20 mmol) of caprolactam, 1.89 g(21 mmol) of dimethyl carbonate, and 54 mg (1.0 mmol) of sodiummethoxide. The mixture was immersed in a 130° C. oil bath and heated for1 hour. After cooling to room temperature the mixture was diluted with100 mL of methylene chloride and to it was added 0.67 g (11.2 mmol) ofacetic acid. Filtration and solvent removal by rotary evaporation,followed by further solvent removal in vacuo (<1 mm) at 95° C. gave theproduct as a yellow paste. H NMR (CDCl₃) indicated the presence ofcompounds I and J in an approximately 80:20 mole ratio.

The lower temperature reaction of these reactants gives little or nocompound J.

The synthesis of a mixture of Compounds E and F, G and H. and I and Jshow that, especially at higher temperatures, the multifunctionalcarbonyl compound can be formed by nucleophilic acyl addition of alactam anion at the carbonyl of a carbonate to produce an intermediatefollowed by reaction of a second lactam anion at the lactam carbonyl ofthe intermediate. The resulting multifunctional carbonyl compounds canthen be reacted with a 4-aminopiperidine radical to provide a HALSmixture which is an effective stabilizer. Generally the product producedin the lower temperature reactions are less colored.

Example 1 Preparation of 2,2,6,6-Tetramethylpiperidin-4-yl6-(2,2,6,6-tetramethyl-4-piperidinoxycarbonyl Amino)hexanoate (CompoundI)

To a 500 mL three-necked flask equipped with a magnetic stirrer, aDean-Stark trap with a condenser, a thermometer, and a glass stopper wasadded 20 g (98.4 mmol) of Compound A, 46.3 g (0.295 mol) of2,2,6,6-tetramethyl-4-piperidinol, and 150 mL of toluene. Under a slownitrogen flow, 20 mL of toluene was distilled off and the trap drained.The glass stopper was removed and 1.0 g (1.67 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added. Another 75 mL oftoluene was slowly distilled off over 8 hours. After addition of another110 mL of toluene, 80 mL of toluene was removed over an additional 2hours. The degree of conversion by NMR analysis was >98%. The mixturewas cooled to room temperature and diluted with ether. The organicsolution was washed with water to remove excess amino alcohol and driedover sodium carbonate. Filtration and removal of solvent under reducedpressure followed by further solvent removal in vacuo (<1 mm) at 95° C.gave 41.2 g (92%) of Compound I as an white solid, m.p. 59-62° C. Thestructure of the material was confirmed by ¹H NMR analysis. ¹H NMR(CDCl₃): δ 5.19 (m, 1H, R₂CH—OCOCH₂—); 5.05 (m, 1H, R₂CHOCONH—); 4.63(br s, 1H, NH); 3.17 (br dt, 2H, —CH ₂—NH—); 2.28 (t, 2H, —CH₂COO);2.00-1.30 (m, 14H, CH ₂C(CH₃)₂, CH(CH ₂)₃CH₂, 1.20 (d, 24H, CH₂C(CH₃)₂).

Example 2 Preparation of 1,2,2,6,6-Pentamethylpiperidin-4-yl6-(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonylamino)hexanoate (CompoundII)

To a 100 mL three-necked flask equipped with a magnetic stirrer, aDean-Stark trap with a condenser, a thermometer, and a glass stopper wasadded 4.85 g (23.9 mmol) of Compound A, 12.2 g (71.6 mmol) of1,2,2,6,6-pentamethyl-4-piperidinol, and 30 mL of toluene. Under a slowargon flow, 17 mL of toluene was distilled off and the trap drained. Theglass stopper was removed and 0.26 g (0.43 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added. Another 22 mL oftoluene was slowly distilled off over 1 hour. After addition of another10 mL of toluene, 11 mL of toluene was removed over an additional 3hours. The degree of conversion by NMR analysis was >97%. The mixturewas cooled to room temperature and diluted with ethyl acetate. Theorganic solution was washed with water to remove excess amino alcoholand dried over magnesium sulfate. Filtration and removal of solventunder reduced pressure followed by further solvent removal in vacuo (<1mm) at 95° C. gave 10.23 g (89%) of Compound II as a nearly colorlessviscous oil. The structure of the material was confirmed by ¹H NMRanalysis. ¹H NMR (CDCl₃): δ 5.03 (m, 1H, R₂CH—OCOCH₂—); 4.92 (m, 1H,R₂CHOCONH—); 4.68 (br s, 1H, NH); 3.18 (br dt, 2H, —CH ₂—NH—); 2.28 (t,2H, —CH₂COO—); 2.23 (s, 3H, CH₃NC(CH₃)₂); 1.90-1.35 (in, 14H, CH₂(CH₂)₃CH₂, CH ₂C(CH₃)₂), 1.13 (d, 24H, CH₂C(CH ₃)₂). The TGA T-10% value ofCompound II was 237° C.

Example 3 Preparation of 2,2,6,6-Tetramethylpiperidin-4-yl6-(2,2,6,6-tetramethyl-4-piperidinoxycarbonylamino)undecanoate (CompoundIII).

A 250 mL single-necked reaction flask was equipped with a magneticstirrer and a distillation head fitted with a thermometer, condenser,and receiving flask with a nitrogen inlet and outlet to a bubbler. Tothis flask was charged 4.3 g (11.57 mmol) of Compound B, 7.27 g (46.3mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and 200 mL of xylene. Undera slow nitrogen flow, 25 mL of xylene was distilled off and the trapdrained. After lowering the heat source and allowing the mixture to coolto 110° C., 0.17 g (0.28 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heatsource raised. Another 290 mL of xylenes were slowly distilled off over7 hours, charging 100 mL of xylenes at the 3 hour point. After additionof another 240 mL of xylenes, distillation was continued for another 12hours, during which time 175 mL was collected. NMR analysisindicated >90% conversion. The mixture was cooled to room temperatureand diluted with ether. The organic solution was washed with water toremove excess amino alcohol and dried over magnesium sulfate. Filtrationand removal of solvent under reduced pressure followed by furthersolvent removal in vacuo (<1 mm) at 95° C. gave 5.5 g (83%) of CompoundIII as a yellow oil. The structure of the material was confirmed by ¹HNMR analysis. ¹NMR (CDCl₃): δ 5.19 (m, 1H, R₂CH—OCOCH₂—); 5.06 (m, 1H,R₂CHOCONH—); 4.62 (br s, 1H, NH); 3.17 (br dt, 2H, —CH ₂—NH—); 2.25 (t,2H, —CH₂COO); 2.00-1.20 (m, 26H, CH ₂C(CH₃)₂, CH₂(CH ₂)₉CH₂), 1.20 (d,24H, CH₂C(CH ₃)₂).

Example 4 Preparation of 1,2,2,6,6-Pentaamethylpiperidin-4-yl6-(1,2,2,6,6-pentamethyl-4-piperidinoxycarbonylamino)undecanoate(Compound IV)

A 250 mL single-necked reaction flask was equipped with a magneticstirrer and a distillation head fitted with a thermometer, condenser,and receiving flask with a nitrogen inlet and outlet to a bubbler. Tothis flask was charged 4.5 g (12.1 mmol) of Compound B, 8.3 g (48.4mmol) of 1,2,2,6,6-pentamethyl-4-piperidinol, and 200 mL of xylene.Under a slow nitrogen flow, 25 mL of xylene was distilled off and thetrap drained. After lowering the heat source and allowing the mixture tocool to 110° C., 0.19 g (0.31 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added. Another 450 mLof xylenes were distilled off over 24 hours, adding 100 mL, 100 mL and150 mL at the 5, 21 and 23 hour points, respectively. The mixture wascooled to room temperature and diluted with ether. The organic solutionwas washed with water to remove excess amino alcohol, followed bywashing with aqueous NaOH and then more water, and finally dried overmagnesium sulfate. Filtration and removal of solvent under reducedpressure followed by further solvent removal in vacuo (<1 mm) at 95° C.gave 5.4 g (79%) of Compound IV as a nearly colorless oil. The structureof the material was confirmed by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.05(m, 1H, R₂CH—OCOCH₂—); 4.94 (m, 1H, R₂CHOCONH—); 4.65 (br s, 1H, NH);3.16 (br dt, 2H, —CH ₂—NH—); 2.25 (t, 2H, t, 2H, —CH₂COO—); 2.23 (5, 3H,CH₃NC(CH₃)₂); 1.90-1.28 (m, 26H, CH₂(CH ₂)₉CH₂, CH ₂C(CH₃)₂), 1.10 (d,24H, CH₂C(CH ₃)₂).

Example 5 Preparation of 2,2,6,6-Tetramethylpiperidin-4-yl6-[(2,2,6,6-tetramethyl-4-piperidinyloxy)oxoacetyl]amino Hexanoate(Compound V)

A 250 mL single-necked reaction flask was equipped with a magneticstirrer and a Dean-Stark trap fitted with a condenser and nitrogeninlet/outlet. The flask was charged with 10.0 g (43.3 mmol) of compoundC, 20.4 g (130 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and 150 mL oftoluene. Under a slow nitrogen flow, 15 mL of toluene was distilled offand the trap drained. After lowering the heat source and allowing themixture to cool to 110° C., 0.46 g (0.76 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heatsource raised. Another 110 mL of toluene was slowly distilled off over 9hours, then 25 mL of xylenes were added and 20 mL of additional solventdistilled off over 6 hours. The resulting mixture was cooled to roomtemperature and diluted with ethyl acetate. The organic solution waswashed with water to remove excess amino alcohol and dried overmolecular sieves. Filtration and removal of solvent under reducedpressure followed by further solvent removal in vacuo (<1 mm) at 95° C.gave 13.0 g (62%) of Compound V as a yellow oil. The structure of thematerial was confirmed by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 7.15 (m,1H, NHCO—); 5.32 (m, 1H, R₂CHOCO—); 5.20 (m, 1H, R₂CHOCO—); 3.38 (dt,2H, —CH ₂—NH—); 2.28 (t, 2H, —CH₂COO—); 2.05-1.10 (m, 14H, CH₂(CH₂)₃CH₂), CH ₂C(CH₃)₂), 1.20 (d, 12H, CH₂C(CH ₃)₂); 1.18 (d, 12H, CH₂C(CH₃)₂).

Example 6 Preparation of 2,2,6,6-Tetramethylpiperidin-4-yl6-(Octanoylamino)hexanoate (Compound VI)

A 250 mL single-necked reaction flask was equipped with a magneticstirrer and a Dean-Stark trap fitted with a condenser and nitrogeninlet/outlet. To this flask was charged 6.1 g (22.5 mmol) of compound D,5.29 g (33.7 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and 150 mL oftoluene. Under a slow nitrogen flow, 8 mL of toluene was distilled offand the trap drained. After lowering the heat source and allowing themixture to cool to 110° C., 0.17 g (0.28 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heatsource raised. Another 100 mL of toluene was slowly distilled off over16 hours and the resulting mixture was cooled to room temperature anddiluted with methylene chloride. The organic solution was washed withwater to remove excess amino alcohol and dried over anhydrous sodiumcarbonate. Filtration and removal of solvent under reduced pressurefollowed by further solvent removal in vacuo (<1 mm) at 60° C. gave 8.0g (90%) of Compound VI as a light brown wax. The structure of thematerial was confirmed by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.60 (m,1H, NHCO—); 5.18 (m, 1H, R₂CHOCO—); 3.25 (dt, 2H, —CH ₂—NH—); 2.28 (t,2H, —CH₂COO—); 2.16 (t, 2H, —CH₂CONH—); 1.95-1.10 (m, 20H, CH₂(CH₂)₃CH₂, CH₂(CH ₂)₅, CH₂CH₂C(CH₃)₂); 1.20 (d, 12H, CH₂C(CH ₃)₂; 0.88 (t,3H, —CH₂CH ₃).

Example 7 Synthesis of Oligomeric HALS Compounds (Compounds VII andVIII)

To a 100 ml 3-necked round bottom flask equipped with a magneticstirrer, a thermometer and a Dean-Stark trap fitted with a condenser anda nitrogen inlet/outlet to a bubbler was charged 5.45 g (26.8 mmol) ofCompound A, 27 mL of toluene, 163 mg (0.27 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane, and 5.4 g ofN-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol. The mixture washeated so that 13 mL of solvent distilled off over three hours. A 12 mLaliquot was removed from the reaction mixture (Fraction A), and wasworked up as described below. The remaining reaction mixture was heatedfor an additional 2.5 hours, over which time 8 mL of solvent distilledoff. After addition of 10 mL of xylenes, the temperature was increasedso that 15 mL of additional solvent distilled off over 3 hours. Theresulting reaction mixture (Fraction B) was worked up as describedbelow.

Workup of Fraction A: The 12 mL aliquot was diluted with methylenechloride, washed with water, dried (MgSO₄), filtered, and the solventremoved under reduced pressure. Further solvent removal in vacuo (<1 mm)at 50-60° C. gave 4.4 g of compound VII as a clear colorless semisolid.High Performance Size-Exclusion Chromatography (HPSEC) gave a value of2,000 for the number average molecular weight (Mn) of the material usinga polystyrene standard. The structure of the material was confirmed by¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.07 (m, 0.5H, R₂CHOCOCH₂—); 4.94 (m,0.5H, R₂CHOCONH—); 4.65 (br s, 1H, NH); 3.92 (app q, 2H, —CH ₂—OCOCH₂,—CH ₂—OCONH ₃—); 3.68 (s, 0.44H, —CH₂COOCH₃); 3.66 (s, 0.44H, —NHCOOCH₃); 3.18 (br m, 2H, —CH ₂—NH—); 2.65 (t, 2H, CH₂CH ₂—N); 2.28 (app q,2H, CH₂COO—); 1.90-1.30 (m, 12H, CH₂(CH ₂)₃CH₂), CH ₂C(CH₃)₂), 1.10CH₂C(CH ₃)₂).

Workup of Fraction B: The remainder of the reaction mixture was dilutedwith methylene chloride, washed with water, dried (MgSO₄), filtered, andthe solvent removed under reduced pressure. Further solvent removal invacuo (<1 mm) at 80-90° C. gave 4.6 g of compound VIII as a white foam.High Performance Size-Exclusion Chromatography (HPSEC) gave a value of8,800 for the number average molecular weight (Mn) of the material usinga polystyrene standard. The structure of the material was confirmed by¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.07 (m, 0.5H, R₂CH—OCOCH₂—); 4.94(m, 0.5H, R₂CHOCONH—); 4.65 (br s, 1H, NH); 3.92 (app q, 2H, —CH₂—OCOCH₂, —CH ₂—OCONH—); 3.68 (s, 0.16H, —CH₂COOCH ₃); 3.66 (s, 0.16H,—NHCOOCH ₃; 3.18 (br m, 2H, —CH ₂—NH—); 2.65 (t, 2H, CH₂—CH ₂—N); 2.28(app q, 2H, —CH₂COO—); 1.90-1.30 (m, 12H, CH₂(CH ₂)₃CH₂), CH ₂C(CH₃)₂),1.10 (d, 12H, CH₂C(CH ₃)₂).

Example 8 Single Step Reaction to Produce2,2,6,6-Tetramethyl-4-piperidine6-(2,2,6,6-Tetramethyl-4-piperidinoxycarbonyl Amino)hexanoate (CompoundI), Base Catalyzed

To a 100 mL three-necked round bottom flask equipped with a magneticstir bar, an addition funnel containing anhydrous toluene, and aDean-Stark trap fitted with a condenser and a nitrogen inlet/outlet, wascharged 1.69 g (15 mmol) of caprolactam, 2.74 g (15.75 mmol) of dibutylcarbonate, 4.94 g (31.5 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and50 mL of toluene. The mixture was heated to a heating mantle temperatureof 142° C., so that 6 mL of solvent distilled into the trap. The mixturewas cooled and 75 mg (1.39 mmol) of sodium methoxide was added to themixture. The mixture was reheated to boiling and 20 mL distilled intothe trap over 4 hours. The trap was drained and 25 mL of toluene wasadded to the mixture through the addition funnel. After another 25 mL ofsolvent distilled off over 4 hours, 25 mL of anhydrous xylenes wasadded, and 35 mL of solvent removed over 6 hours. ¹H NMR indicated >95%conversion of starting material. Cooling to room temperature, dilutionwith methylene chloride, washing with water, drying (molecular sieves),filtration, and removal of solvent under reduced pressure gave a yellowoil. Further removal of volatiles at 90° C./0.8 mm gave 5.0 g, 75%yield, of a light yellow semisolid. ¹H NMR indicated the presence of thedesired hindered amine, compound I, with approximately 85% purity.

Example 9 Single Step Reaction to Produce2,2,6,6-Tetramethyl-4-piperidine6-(2,2,6,6-Tetramethyl-4-piperidinoxycarbonyl Amino)hexanoate (Compound1), Lewis Acid Catalyzed

To a 250 mL three-necked round bottom flask equipped with a magneticstir bar, and a Dean-Stark trap fitted with a condenser and a nitrogeninlet/outlet, was charged 16.9 g (150 mmol) of caprolactam, 39.2 g (225mmol) of dibutyl carbonate, 70.65 g (450 mmol) of2,2,6,6-tetramethyl-4-piperidinol, and 200 mL of toluene. The mixturewas heated to a pot temperature of 120° C., so that 12 mL of solventdistilled into the trap. The mixture was cooled, and 0.85 g (3 mmol) oftitanium (IV) isopropoxide was added to the mixture. The mixture wasreheated to boiling and the pot temperature gradually increased from120° C. to 210° C. so that solvent distilled off over 20 hours. ¹H NMRindicated >95% conversion of starting material. The trap was removed andthe flask fitted with a distillation head and a condenser with a steamjacket. A solid impurity (28.0 g) distilled over at 75-120° C./0.8 mm.The flask residue was diluted with methylene chloride and to it wasadded 0.3 mL of water. Overnight stirring at room temperature,filtration, and removal of solvent gave 59.0 g (89% yield) of a thick,light yellow oil. ¹H NMR indicated the presence of the desired hinderedamine I with approximately 90% purity. To this oil was added 30 ghexanes and the mixture heated until homogeneous. After cooling to 5° C.and standing 12 hours at this temperature, filtration afforded 36 g (53%yield) of the desired hindered amine I as a white solid, mp 51-54° C.,with a purity by ¹H NMR of approximately 95%.

Example 10 Preparation of Oligomeric HALS from BPIP and Compound ACompound (IX)

To a 250 mL 3-necked round bottom flask equipped with a magneticstirrer, a thermometer, and a Dean-Stark trap fitted with a condenserand nitrogen inlet/outlet to a bubbler, was charged 5.0 g (24.6 mmol) ofCompound A, 100 mL of mixed xylenes, and 9.69 g (24.6 mmol) ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine (BPIP).The mixture was heated to reflux for one hour, after which the heatsource was lowered, the Dean-Stark trap drained of 30 mL of xyleneswhich had collected, and 0.22 g (0.37 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added. The mixture wasreheated to the boiling point, and another 50 mL of solvent was allowedto collect over several hours. Another 100 mL portion of anhydrousxylenes was added and distilled off over several hours. The mixture wascooled to room temperature, diluted with methylene chloride, washed withwater, dried (molecular sieves), filtered and the solvent removed underreduced pressure to give 12.1 g of compound IX as a tacky yellowishsolid.

wherein i and j are integers and the sum of i and j is greater than orequal to 2. The structure of compound IX was confirmed with ¹H NMRanalysis. ¹H NMR (CDCl₃): δ 4.58 (br m, NH); 4.35 (m, R₂CHNR₂); 3.65 (s,CH₃O—); 3.25 (app q, —CH ₂—NH—); 3.00 (app q, —CH ₂—NRCO—); 2.89 (m,R₂CHNHR); 2.37 (t, 2H, —CH₂COO); 1.90-0.89 (m, N—CH₂(CH2)₄CH ₂—N,COCH₂(CH ₂)₃CH₂NH, CH ₂C(CH₃)₂, CH₂C(CH₃)₂).

Example 11 Single Step Reaction to Produce Oligomeric HALS fromCaprolactam, N-Hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinol, andDibutyl Carbonate

To a 50 ml three-necked reaction flask, equipped with a magnetic stirrerand a Dean-Stark trap fitted with a condensor and nitrogen inlet/outlet,was charged 1.0 g (4.97 mmol) ofN-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinol, 0.56 g (4.97 mmol) ofcaprolactam, 0.86 g (4.97 mmol) of dibutyl carbonate, 30 mL of toluene,and 40 mg (0.75 mmol) of sodium methoxide. The flask was immersed in anoil-bath and heated so that the solvent was distilled off over 4 hours.20 mL of xylenes was then added to the reaction mixture and 20 mL ofadditional solvent distilled off over 4 hours. The resulting mixture wascooled to room temperature and diluted with dichloromethane. The organicsolution was washed with water, dried (MgSO₄), and filtered. The solventwas then removed under reduced pressure using a rotary evaporator andfurther removed under vacuum (<1 mm of Hg) at 95° C. to give 1.5 g (88%)of compound VII. The structure of compound VII was confirmed by ¹H NMR.

Example 12 Low Temperature Synthesis of Compound A

To a 250 mL three-neck round bottom flask equipped with a magneticstirrer, a ground glass stopper, a condenser and nitrogen inlet, and athermometer was placed 50.33 g (558 mmol) of dimethyl carbonate and 1.04g (19.3 mmol) of sodium methoxide. The mixture was cooled to 15° C. and21.8 g (193 mmol) of caprolactam was added. The mixture was stirred withintermittent cooling to maintain the reaction temperature between about9 and 18° C. for 45 minutes, then 2.4 g (40 mmol) of glacial acetic acidwas added at <19° C. The mixture was dissolved in 100 mL of methylenechloride and the organic layer extracted with water, dried (MgSO₄),filtered, and the solvent removed under reduced pressure, followed byfurther removal in vacuo (<1 mm of Hg) at 95° C. 39.0 g (99%) ofCompound A was recovered as a nearly colorless oil.

Example 13 Preparation of HALS Mixtures By Reaction of2,2,6,6-Tetramethyl-4-piperidinol and a Mixture of Compounds E and F

A 250 mL 3-necked reaction flask was equipped with a magnetic stirrer, athermometer adapter, and a distillation head fitted with a condenser, areceiver, and a nitrogen inlet/outlet. To this flask was charged 4.3 g(10.45 mmol) of the E/F mixture generated above, 7.27 g (46.3 mmol) of2,2,6,6-tetramethyl-4-piperidinol, and 200 mL of xylenes. Under a slownitrogen flow, 10 mL of xylenes were distilled off and the trap drained.After lowering the heat source and allowing the mixture to cool to 110°C., 0.17 g (0.28 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxanewas added and the heat source raised. Another 172 mL of xylenes wereslowly distilled off over 12 hours. The resulting mixture was cooled toroom temperature and diluted with ethyl acetate. The organic solutionwas washed with water to remove excess amino alcohol and dried overmolecular sieves. Filtration and removal of solvent by rotaryevaporation, and further solvent removal in vacuo (<1 mm) at 95° C. gave5.6 g (93%) of composition M-I as a yellow oil. The structure of thecompounds in the mixture was verified by ¹H NMR analysis. ¹H NMR(CDCl₃): δ 5.41 (br s, NH); 5.19 (m, R₂CH—OCOCH₂—); 5.06 (m,R₂CHOCONH—); 4.62 (br s, NH); 3.22 (dt, —CH ₂—NH—); 3.17 (br dt, —CH₂—NH—); 2.25 (t, —CH₂COO); 2.00-1.20 (m, CH ₂C(CH ₃)₂, CH₂(CH₂)₉CH₂),1.20 (d, CH₂C(CH ₃)₂).

Example 13 Preparation of HALS Mixtures By Reaction of1,2,2,6,6-Pentamethyl-4-piperidinol and a Mixture of Compounds E and F

A 500 mL 3-necked reaction flask was equipped with a magnetic stirrer, athermometer adapter, and a distillation head fitted with a condenser, areceiver, and a nitrogen inlet/outlet. To this flask was charged 7.9 g(19.2 mmol) of the E/F mixture generated above, 14.5 g (85.04 mmol) of1,2,2,6,6-pentamethyl-4-piperidinol, and 300 mL of xylenes. Under a slownitrogen flow, 100 mL of xylenes were distilled off and the trapdrained. After lowering the heat source and allowing the mixture to coolto 100° C., 0.34 g (0.56 mmol) of1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane was added and the heatsource raised. Another 160 mL of xylenes were slowly distilled off over10 hours. After addition of another 20 mL portion of xylenes, heatingwas continued for 8 hours, over which time 32 mL of xylenes werecollected. The resulting mixture was cooled to room temperature anddiluted with methylene chloride. The organic solution was washed withwater to remove excess amino alcohol and dried over MgSO4. Filtrationand removal of solvent by rotary evaporation, and further solventremoval in vacuo (<1 mm) at 95° C. gave 11.2 g (96%) of composition M-IIas a yellow oil. The structure of the compounds in the mixture wasverified by ¹H NMR analysis. ¹H NMR (CDCl₃): δ 5.42 (br s, 1H, NH); 5.05(m, R₂CH—OCOCH₂—); 4.94 (m, R₂CHOCONH—); 4.65 (br s, NH); 3.22 (dt, —CH₂—NH—); 3.16 (br dt, —CH ₂—NH—); 2.25 (t, —CH₂COO—); 2.23 (s,CH₃NC(CH₃)₂); 1.90-1.28 (m, CH₂(CH ₂)₉CH₂,CH ₂C(CH₃)₂), 1.10 (d, CH₂C(CH₃)₂).

PERFORMANCE OF HALS COMPOUNDS ACCORDING TO THE PRESENT INVENTIONExamples 15-21 Weathering Performance of 2 k Acrylic Urethane Clear CoatComposition Containing 1,2,2,6,6-Pentamethyl-4-piperidine6-(1,2,2,6,6-Pentamethyl-4-piperidinoxycarbonylamino)hexanoate (CompoundII)

Compound II (1% based on total resin solids) was pre-dissolved in thesolvent mixture (5-10% solids) and added to the clear 2 k acrylicurethane formulation given in Table I. The 2 k acrylic urethane is atwo-component urethane formed by reacting a hydroxy functional acrylicpolymer with an isocyanate cross linker. Components I and II were mixedjust before use. The clear coats were applied to cold roll steel panels,measuring 4″×12″ and pre-coated with an E-coat primer and whitebase-coat, obtained from ACT Laboratories, Inc. of Hillsdale, Mich. Thedraw-down technique, using WC-60 WIRE-CATORS™ available from Leneta Co.of Ho-Ho-Kus, N.J., was used to apply the clear coat to the pre-coatedpanels. The clear coats were allowed to flash for 10 min at ambienttemperature and cured for 30 min. at 120° C.

TABLE I Acrylic Urethane Clear Coat Formulation Raw Material AmountComponent I JONCRYL ® CDX-588 Acrylic Resin^(a) 100 parts T-12 (2%Solids in Catalyst Solution)^(b)  5 parts Solvent Mixture  45 partsCompound II  1 part^(c) Component II DESMODUR ® N-3390 (90% Solids)^(d) 33 parts Solvent Mixture  17 parts Catalyst Solution T-12 (Dibutyltindilaurate)^(b)  1 part Acetic Acid  4 parts Propylene glycol methylether acetate  45 parts Solvent Mixture: Xylenes  1 part Propyleneglycol methyl ether acetate  1 part Methyl amyl ketone  1 part^(a)JONCRYL is commercially available from S.C. Johnson and Sons Inc. ofRacine, WI. ^(b)T-12 is commercially available from Air Products ofAllentown, PA. ^(c)1% based on total resin solids ^(d)DESMODUR iscommercially available from Bayer Corp. of Pittsburg, PA.

Accelerated weathering was carried out on the coatings with a QUVAccelerated Weather Tester device (commercially available from Q PanelLaboratory Products of Cleveland, Ohio) equipped with UVA-340fluorescent bulbs and with an Atlas Ci65 WeatherOmeter (“Xenon WOM”)(commercially available from Atlas Electronic Devices Co., Chicago,Ill.) equipped with Xenon arc lamps following the SAE J1960 automotiveexterior test protocol. Natural weathering was carried out using 5 degSouth direct weathering in South Florida. Specular properties (gloss anddistinctness of image, or DOI), total color change (Delta E), andyellowing (Delta b) were measured as a function of weathering time.Specular properties were determined as described in ASTM E284 and D253.Color change and yellowing were determined as described in ASTM D2244.

The performance of Compound II under QUV weathering is summarized inExamples 15-17. The effect of Compound II on gloss retention is given inExample 15, the effect on DOI retention is given in Example 16, and theeffect on delta E is given in Example 17.

Example 15 QUV Weathering (UVA-340 Bulbs) of a 2 k Acrylic UrethaneClear Coat Stabilized with Compound II, Effect on Percent GlossRetention

Exposure (hours) Stabilizer 1527 2500 3006 3508 4014 4495 5000 5500 60026500 7011 None 102 86 91.9 72.2 65.1 49.9 41.7 42.2 34.0 33.8 2.1Compound 102 96.8 98.7 99.7 99.6 98.9 101 99.3 100 99.9 96.2 II

A 2 k acrylic urethane clear coat stabilized with 1% of Compound IIshowed superior percent gloss retention compared to the 2 k urethaneclear coat containing no stabilizer.

Example 16 QUV Weathering (UVA-340 Bulbs) of a 2 k Acrylic UrethaneClear Coat Stabilized with Compound II, Effect on Percent DOI Retention

Exposure (hours) Stabilizer 1527 2500 3006 3508 4014 4495 5000 5500 60026500 7011 None 101 97.4 83.7 45.3 26.1  14 12.9 12.7 8.4 9.1 0.1Compound 102 101 101 102 106 106 107 107 107 107 107 II

A 2 k acrylic urethane clear coat stabilized with 1% of Compound IIshowed superior percent DOI retention compared to the a 2 k urethaneclear coat containing no stabilizer.

Example 17 QUV Weathering (UVA-340 Bulbs) of a 2 k Acrylic UrethaneClear Coat Stabilized with Compound II, Effect on Delta E

Exposure (hours) Stabilizer 473 1527 3006 4014 5000 6002 None 1.19 1.993.29 3.51 4.01 4.41 Compound II 0.39 0.63 1.22 1.22 1.36 1.73

A 2 k acrylic urethane clear coat stabilized with 1% of Compound II hada superior effect on total color change (Delta E) compared to the a 2 kurethane clear coat containing no stabilizer. An increase in Delta Eindicates an unfavorable discoloration of the urethane coat.

In addition to the above properties, a visual evaluation of blisteringwas done. After about 7011 hrs, the unstabilized coating was completelydelaminated while the coating containing Compound II showed no signs ofblistering.

The performance of Compound II under Xenon WOM weathering is summarizedin Examples 18-20. The effect of Compound II on gloss retention is givenin Example 18, the effect of Compound II on DOI retention is given inExample 19, and the effect on delta E is given in Example 20. The effectof Compound II under natural weathering (Florida) on gloss retention,yellowing (delta b), and total color change (delta E) is given inExample 21.

Example 18 Xenon Weathering (SAE J1960 Automotive Exterior) of a 2 kPolyurethane Acrylic Coating Stabilized with Compound II, Effect onPercent Gloss Retention

Exposure (hours) Stabilizer 485 987 1513 2011 2517 2947 3539 4039 None97.3 94.5 95.9 90.6 76.4 64.2 47.3 34.5 Compound II 96.5 95.0 95.4 96.092.7 84.7 73.1 62.4

A 2 k acrylic urethane clear coat stabilized with 1% of Compound IIshowed superior gloss retention compared to the a 2 k urethane clearcoat containing no stabilizer.

Example 19 Xenon Weathering (SAE J1960 Automotive Exterior) of a 2 kPolyurethane Acrylic Coating Stabilized with Compound II, Effect onPercent DOI Retention

Exposure (hours) Stabilizer 485 987 1513 2011 2517 2947 3539 4039 44435003 None 104 101 101 96.4 86.5 76.7 54.2 36.6 24.1 16.6 Compound 101102 101 101 100 99.6 96.0 93.8 89.0 75.3 II

A 2 k acrylic urethane clear coat stabilized with 1% of Compound IIshowed superior percent DOI retention compared to the a 2 k urethaneclear coat containing no stabilizer.

Example 20 Xenon Weathering (SAE J1960 Automotive Exterior) of a 2 kPolyurethane Acrylic Coating Stabilized with Compound II, Effect onDelta E

Exposure (hours) Stabilizer 485 987 1513 2011 2517 2947 3539 4039 44435003 None 0.90 1.08 1.42 2.10 2.42 3.31 3.30 3.68 3.78 4.28 Compound0.42 0.54 0.51 1.06 1.08 2.29 2.24 2.44 2.41 2.45 II

A 2 k acrylic urethane clear coat stabilized with 1% of Compound II hada superior effect on total color change (Delta E) compared to the a 2 kurethane clear coat containing no stabilizer. An increase in Delta Eindicates an unfavorable discoloration of the urethane coating.

In addition, to the above properties a visual evaluation of the degreeof cracking was done after 5003 hrs. On a scale of 0 to 5, with 0 beingthe best, the unstabilized coating was rated 5 (severe cracking), whilethe coating stabilized with 1% Compound II was rated 1 (very slightcracking).

Example 21 Florida Weathering (50° South, Direct, 18 Months) of a 2 kAcrylic Urethane Clear Coat Stabilized with Compound II, Effect on GlossRetention, Yellowing (Delta b), and Total Color Change (Delta E)

Stabilizer % Gloss Delta b Delta E None 93 0.61 0.73 Compound II (1%) 960.13 0.25

Under natural weathering conditions a 2 k acrylic urethane clear coatstabilized with 1% Compound II showed superior performance in glossretention, yellowing, and total color change compared to the a 2 kurethane clear coat containing no stabilizer. An increase in Delta Eindicates an unfavorable discoloration of the urethane coating. Anincrease in Delta b indicates an unfavorable yellowing of the urethanecoating.

Example 22 Comparison of Compound II to Conventional HALS Compounds in aPolypropylene Article

Compound III and several commercially available HALS compounds were eachdry blended at a 0.25% loading level into PROFAX 6501 polypropylenepowder containing 0.1% 2,4,6-tri-t-butylphenol (commercially availablefrom Montell USA, Inc. of Wilmington, Del.). The blends were milled witha steam double roller mill at 160-170° C. for four minutes at 25 rpm.The samples were then compression molded into films at 200° C. for threeminutes at a maximum pressure of 30 tons. The sample thicknesses for theexposure tests were measured for each film and fell in the range between2.0 and 2.5 mils. The samples were exposed in a dry Xenon weatherometerand a 120° C. oven. Sample degradation was followed by measurements ofthe increase in the intensity of the carbonyl absorption using aPerkin-Elmer 1310 infrared spectrophotometer available from Perkin-ElmerCorp. of Norwalk, Conn. Percent carbonyl development was expressedaccording to the following relationship:

% Carbonyl development=(A_(x)−A_(o))/a*l

where A_(o)=absorbance at 5.85 microns less absorbance at 5.35 micronsfor the unexposed film

A_(x)=absorbance at 5.85 microns less absorbance at 5.35 microns for theexposed film

a=0.20 (absorptivity for “carbonyl” in polypropylene)

l=film thickness in mils

The exposure endpoint was defined as exposure hours required to reach a0.1% carbonyl development level. The data in Table II provide acomparison of Compound II with a variety of other commercially availableHALS compounds.

TABLE II Performance of HALS compounds in PROFAX 6501 Polypropylene.HALS Compound in PROFAX 6501 Dry XeWOM Oven 120° C. Sample IDPolypropylene (hours)^(a) (days)^(a) A CYASORB ® 1320 36 UV-3346^(b) BCHIMASORB ® 944^(c) 1690 51 C TINUVIN ® 783^(c)  987 51 D UVASORB ®HA-88^(d) 1900 51 E UV-CHEK ® >2000  11 AM-340^(e) F TINUVIN ® 770^(c)1200-1600 7 G TINUVIN ® 765^(c) 1200-1600 14 H Compound II >2000  11 IN/A <400 9 ^(a)Average of two samples, 2.5 mils ^(b)A product of CytecIndustries, Inc. of West Paterson, NJ ^(c)A product of Ciba SpecialtyChemicals, Inc. of Hawthorne, NY ^(d)A product of 3 V Inc. ofGeorgetown, SC ^(e)A product of Ferro Corporation of Cleveland, OH

The data in Table II demonstrate that Compound II outperformed theunstabilized system and showed equal or superior performance compared tothe other HALS compounds tested after 2000 hours exposure in the XeWOM.

COMPARISON OF HALS COMPOUNDS OF THE PRESENT INVENTION TO CONVENTIONALHALS Example 23 Performance of Compounds I-IV, VII, and VIII Relative toConventional HALS in a PROFAX 6501 Polypropylene Article

Compounds I-IV, VII, and VIII, as well as several commercially availableHALS compounds, were each dry blended at a 0.2 percent loading levelinto a PROFAX 6501 polypropylene powder (commercially available fromMontel USA Inc. of Wilmington, Del.) containing 0.07 percent calciumstearate (commercially available from Witco Corp. of Greenwich, Conn.),and 0.07 percent Cyanox A-2777 (commercially available from CytecIndustries of West Paterson, N.J.). Blended material was melt-mixed in aBrabender PL-2000 torque rheometer base (commercially available fromC.W. Brabender Inc., South Hackensack, N.J.) equipped with a singlemixing screw extruder-5 zone, single pass at 50-75 rpm, with thetemperature of zones 1-5 at 210° C., 215° C., 220° C., 225° C., and 230°C., respectively. The extrudate was cooled, dried, and pelletized.Pellets were compression molded into sample plaques (2×2.5×0.100 inches)using a PHI press (commercially available from Pasadena Hydraulics Inc.,The City of Industry, Calif.) at 275° C. Sample plaques were exposed inthe xenon-arc weatherometer as determined by ASTM G-26 Standard usingTest Method B with alternate exposure to light and darkness andintermittent exposure to water spray maintaining an atmospheretemperature of 63±3° C. and a relative humidity of 3015 percent (Miami,Fla. conditions). Color (ΔE) was determined with a Macbeth Color EyeColorimeter (commercially available from Gretag-MacBeth LLC of NewWindsor, N.Y.) under laboratory conditions with illuminate C, 2°observer, specular component excluded, and UV component included.Specular gloss was measured according to ASTM D523 Standard using aGardner black plate 60° Glossmeter measuring deviation loss to 50percent. Pellets were also injection-molded into tensile bars using anArburg “Allrounder” hydraulic injection molder (commercially availablefrom Arburg GmbH & Co. of Lossburg, Germany). Temperatures used were asfollows: nozzle, 200° C.; nozzle side, 220° C.; middle, 225° C.; feed,210° C.; and mold, 52° C. The blended material was also made into thinfilms. The thin films were prepared as described in Example 22.

Compounds I-IV, VII, and VIII were compared to Tinuvin 765(bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, CAS #41556-26-7)(commercially available from Ciba Specialties Corp., Hawthorne, N.Y.);Tinuvin 770 (bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, CAS#52829-07-9) (commercially available from Ciba Specialties Corp.,Hawthorne, N.Y.); Tinuvin 622(1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl piperidine-succininicacid, dimethyl ester, copolymer, CAS #65447-77-0) (commerciallyavailable from Ciba Specialties Corp., Hawthorne, N.Y.); Chimasorb 944(poly[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4,-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)-imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino],CAS #71878-19-8) (commercially available from Ciba Specialties Corp.,Hawthorne, N.Y.); Tinuvin 783 (a 1:1 blend of Chimasorb 944 and Tinuvin622) (commercially available from Ciba Specialties Corp., Hawthorne,N.Y.).

Table III shows a comparison of Hours to ΔE=3 and Hours to 50% GlossRetention for polypropylene plaques and Hours to Failure (as measured bycarbonyl development in thin films) for the HALS of the invention andseveral commercially available HALS. Table IV shows a comparison of 50%Strength Retention, 50% Elongation Retention, and Hours to 50% Retentionof Tensil Strength for the HALS of the invention and severalcommercially available HALS compounds in PROFAX polypropylene tensilebars.

TABLE III Performance of HALS of the Invention Relative to ConventionalHALS in PROFAX 6501 Polypropylene Plaques and, Polypropylene Thin Films.Hours to 50% Hours to Contained Hours to ΔE = 3 Gloss Retention Failure*Additive (plaques) (plaques) (thin films) Compound VII 2080 1333 1000Compound VIII 1267 707 600 Tinuvin 622^(a) 529 895 600 None 180 <100 200Compound II 2300 >1600 Compound IV >3000 >1600 800 Tinuvin 765^(a)2740 >1600 600 None 180 <100 200 Compound I 474 >1200 600 Compound III600 >600 1000 Tinuvin 770^(a) 581 >1200 600 None 180 <100 200 *Asmeasured by the increase in carbonyl absorption to a level of 0.1% asdescribed for Example 22. ^(a)A product of Ciba Specialty Chemicals,Inc. of Hawthorne, NY

TABLE IV Performance of HALS of the Invention Relative to ConventionalHALS in PROFAX 6501 Propylene Tensile Bars, Effect of Florida Weatheringand Xenon Weathering. Hours to 50% Retention 50% Strength 50% Elongationof Tensile Retention Retention Strength Contained Months (Florida Months(Florida (Xenon Additive Weathering) Weathering) Weathering) CompoundVII >12 5 Compound VIII 8 5 Tinuvin 622 7 3 None <3 <3 Compound II 840Compound IV 1100 Tinuvin 765 640 None 204 Compound I 384 Compound III690 Tinuvin 770 1000 None 204

The data in Tables III and IV demonstrate that HALS of the inventionoutperformed the unstabilized system and showed equal or superiorperformance compared to the commercially available HALS compounds.

Example 24 Performance of Compounds I-IV, VII-VIII Relative toConventional HALS in Polyethylene Articles

Compounds I-IV and VII-VIII, as well as several commercially availableHALS compounds were each dry blended at a 0.1 percent loading level intoa LLDPE prills (commercially available from Equistar Chemicals LP. ofHouston Tex.) containing 0.01 percent zinc stearate (commerciallyavailable from Malinckrodt Chemicals of St. Louis, Mo.), and 0.07percent Cyanox A-2777 (commercially available from Cytec Industries ofWest Paterson, N.J.). Blended material was melt-mixed in a BrabenderPL-2000 torque rheometer base equipped with a single mixing screwextruder-5 zone, single pass at 50-75 rpm, with the temperature of zones1-5 at 170° C., 175° C., 180° C., 185° C., and 190° C., respectively.The extrudate was cooled, dried, and pelletized. Pellets werecompression molded into sample plaques (2×2.5×0.100 inches) using a PHIpress at 177° C. Sample plaques were exposed in the xenon-arcweatherometer as determined by ASTM G-26 Standard using Test Method Bwith alternate exposure to light and darkness and intermittent exposureto water spray maintaining an atmosphere temperature of 63±3° C. and arelative humidity of 30±5 percent (Miami, Fla. conditions). Color (ΔE)was determined with a Macbeth Color Eye Colorimeter under laboratoryconditions with illuminate C, 2° observer, specular component excluded,and UV component included. The blended material was also made into thinfilms. The thin films were prepared as described in Example 22.

Table V shows a comparison of Hours to ΔE=3 and Hours to 50% GlossRetention and Hours to Failure (as measured by carbonyl development) forthe HALS of the invention and several commercially available HALScompounds in LLDPE plaques and thin films.

TABLE V Performance of HALS of the Invention Relative to ConventionalHALS in LLDPE Plaques and Thin Films. Hours to 50% Hours to ContainedHours to DE = 3 Gloss Retention Failure* Additive (plaques) (plaques)(Thin films) Compound VII 6122 5729 1000 Compound VIII 6831 4900 1800Tinuvin 622 >7600 6212 1000 None 180 2467 200 Compound II >7600 >76002200 Compound IV >7600 6850 1000 Tinuvin 765 >7600 >7600 1000 None 1802467 200 Compound I >7600 7492 >1800 Compound III >7600 7446 >1800Tinuvin 770 600 7252 1800 None 180 2467 200 *As measured by the increasein carbonyl absorption to a level of 0.1% as described for Example 22.

The data in Tables III and IV demonstrate that HALS of the inventionoutperformed the unstabilized system and showed equal or superiorperformance compared to the commercially available HALS compounds.

Example 25 Performance of Compound VIII Relative to Conventional HALS ina Polypropylene Article

Compound VIII, 1:1 blends of Compound VIII with CyasorbR UV-3346,CyasorbR UV-3346, and several commercially available HALS compounds wereeach dry blended at a 0.2% loading level in PROFAX 6501 polypropyleneflake (commercially available from Montel USA Inc. of Wilmington, Del.)containing 0.07 percent calcium stearate (commercially available fromWitco Corp. of Greenwich, Conn.), and 0.07 percent Cyanox A-2777(commercially available from Cytec Industries of West Paterson, N.J.).Blended material was melt-mixed in a Brabender PL-2000 torque rheometerbase (commercially available from C.W. Brabender Inc., South Hackensack,N.J.) equipped with a single mixing screw extruder-5 zone, single passat 50-75 rpm, with the temperature of zones 1-5 at 210° C., 215° C.,220° C., 225° C., and 230° C., respectively. The extrudate was cooled,dried, and pelletized. Pellets were compression molded into sampleplaques (2×2.5×0.100 inches) using a PHI press (commercially availablefrom Pasadena Hydraulics Inc., The City of Industry, Calif.) at 275° C.Sample plaques were exposed in the xenon-arc weatherometer as determinedby ASTM G-26 Standard using Test Method B with alternate exposure tolight and darkness and intermittent exposure to water spray maintainingan atmosphere temperature of 63±3° C. and a relative humidity of 30±5percent (Miami, Fla. conditions). Specular gloss was measured accordingto ASTM D523 Standard using a Gardner black plate 60° Glossmetermeasuring deviation loss to 50 percent.

Example 25 Performance of Compound VIII of the Invention Relative toConventional HALS in PROFAX 6501 Polypropylene Plaques

Hours to 50% Gloss Additive Retention Compound VIII 2450 Cyasorb UV-33462400 1:1 Cyasorb UV-3346:Compound VIII >2850 (1:1) Tinuvin 783 2283Tinuvin 622 2850

The data in Example 25 demonstrates that HALS of the invention showedequal or superior performance compared to commercially available HALScompounds.

Example 26 Performance of Compounds I and II Relative to ConventionalHALS in Nylon 6 Plaques

Compounds I and II and several commercially available HALS compoundswere each dry blended at a 0.3% loading level into B85ZP Nylon 6(commercially available from Honeywell Inc. of Morris Township, N.J.)containing 0.075% Cyanox A-2777 (commercially available from CytecIndustries Inc. of West Paterson, N.J.). The blended material was meltmixed in a Haake SS (commercially available from Haake Inc. (USA) ofParamus, N.J.) 0.75 inch, 25:1 single mixing screw extruder—4 zone,single pass at 70 rpm, with the temperature of zones 1-4 at 245° C.,260° C., 270° C., and 260° C., respectively. The extrudate was cooleddried and pelletized. Pellets were injection molded into sample plaques(2×2.5×0.100 inches) using an Arburg Allrounder 320-210-750 injectionmolding machine (commercially available from Arburg GmbH & Co. ofLossburg, Germany) with the nozzle at 245° C., nozzle side at 260° C.,middle at 270° C., feed at 270° C., and mold at 82° C. Sample plaqueswere exposed in the xenon-arc weatherometer as determined by ASTM G-26Standard using Test Method B with alternate exposure to light anddarkness and intermittent exposure to water spray maintaining anatmosphere temperature of 63±3° C. and a relative humidity of 30±5percent (Miami, Fla. conditions). Color as measured by yellowing index(YI) and ΔE was determined with a Macbeth Color Eye Colorimeter underlaboratory conditions with illuminate C, 2° observer, specular componentexcluded, and UV component included.

Example 26 Performance of Compounds I and H Relative to ConventionalHALS in Nylon 6 Plaques

Additive YI Value after 4000 hours ΔE value UV-3346 6 8.3 UV-3529 5.6 8Nylostab S-EED^(a) 3.3 6.8 Tinuvin 770 3.4 8.3 Compound 1 2.3 7.8Compound II 2.4 7.3 None 8.4 12.3 ^(a)Nylostab S-EED is a developmentalproduct from Clariant Corp. of Charlotte, N.C.;N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)isophthalamide)

The data in Example 26 demonstrates that HALS of the inventionoutperformed the unstabilized system and showed equal or superiorperformance compared to the other HALS compounds.

The invention described and claimed herein is not to be limited in scopeby the specific embodiments herein disclosed, since these embodimentsare intended as illustrations of several aspects of the invention. Anyequivalent embodiments are intended to be within the scope of thisinvention. Indeed, various modifications of the invention in addition tothose shown and described herein will become apparent to those skilledin the art from the foregoing description. Such modifications are alsointended to fall within the scope of the appended claims.

What is claimed is:
 1. A compound having the formula (I):RZ—CO—CR^(a)R^(b)(—CR^(c)R^(d))_(n)−NH—(Y)_(m)—CO—A  (I) wherein n is aninteger from 1 to 15, m is either 0 or 1; R^(a), R^(b), R^(c), and R^(d)are each a hydrogen or a hydrocarbyl group; Y is CO—(CR^(e)R^(f))_(p),wherein R¹ and R^(f) are each a hydrogen or hydrocarbyl group and p iszero or an integer from 1 to 20 or CO—C₆H₄—, wherein the substitutionpattern on the phenylene group is an ortho, meta, or para substitutionpattern and one or more of the hydrogens of the phenylene group may besubstituted by a hydrocarbyl group, or a functional group selected fromhalide, cyano, amino, thio, carboxylate, hydroxyl, sulfonate, nitroso,and nitro groups; Z is —O— or —NG—; wherein G is H, C₁-C₁₂ alkyl or theradical R; wherein R is

wherein R¹ is hydrogen, C₁-C₈ alkyl, O, OH, CH₂CN, C₁-C₁₈ alkoxy, C₁-C₁₈hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₁-C₁₂ hydroxycycloalkoxy, C₃-C₆alkenyl, C₂-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted or substitutedon the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl;R² is hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ are each ahydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal R moieties,which together with the carbon to which they are attached form a C₅-C₁₀cycloalkyl; and A is ZR; wherein the hydrocarbyl group is selected fromthe group consisting of: alkyl, cycloalkyl, aryl, aryalkyl, alkaryl,alkenyl, cycloalkenyl and alkynyl having from about 1 to 24 carbonatoms.
 2. The compound of claim 1, wherein G is H or a C₁-C₁₂ alkyl. 3.The compound of claim 2, wherein R¹ is a H, C₁-C₄ alkyl, , OH, C₁-C₁₈alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂hydroxycycloalkoxy; R² is H, or C₁-C₄ alkyl; R³, R⁴, R⁵, and R⁶ are eachH or C₁-C₄ alkyl; R^(a), R^(b), R^(c), and R^(d), are each a hydrogen,alkyl, cycloalkyl, aryl, aryalkyl, alkaryl or alkenyl having from 1 to24 carbon atoms; and n is from 4 to
 11. 4. The compound of claim 2,wherein R¹ is H or CH₃; R³, R⁴, R⁵, and R⁶ are each CH₃; R² is hydrogen;R^(a), R^(b), R^(c) and R^(d) are each a hydrogen; m is 0 or 1; and n isan integer from 4 to
 10. 5. The compound of claim 2, wherein n is
 4. 6.A compound having the formula (I):RZ—CO—CR^(a)R^(b)—(—CR^(c)R^(d)—)_(n)—NH—(Y)_(m)—CO—A  (I) wherein n isan integer from 1 to 15, m is either 0 or 1; R^(a), R^(b), R^(c), andR^(d) are each a hydrogen or a hydrocarbyl group; Y isCO—(CR^(e)R^(f))_(p), wherein R^(e) and R^(f) are each a hydrogen orhydrocarbyl group and p is zero or an integer from 1 to 20 or CO—C₆H₄—,wherein the substitution pattern on the phenylene group is an ortho,meta, or para substitution pattern and one or more of the hydrogens ofthe phenylene group may be substituted by a hydrocarbyl group, or afunctional group selected from halide, cyano, amino, thio, carboxylate,hydroxyl, sulfonate, nitroso, and nitro groups; Z is —O—, R is

wherein R¹ is hydrogen, C₁-C₈ alkyl, O, OH, CH₂CN, C₁-C₈ alkoxy, C₁-C₁₈hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂ hydroxycycloalkoxy, C₃-C₆alkenyl, C₂-C₁₈ alkynyl, C₇-C₉ phenylalkyl, unsubstituted or substitutedon the phenyl with 1, 2 or 3 C₁-C₄ alkyls, or an aliphatic C₁-C₈ acyl;R² is hydrogen, C₁-C₈ alkyl, or benzyl; R³, R⁴, R⁵, and R⁶ are each ahydrogen, C₁-C₈ alkyl, benzyl or phenethyl, or two geminal R moieties,which together with the carbon to which they are attached form a C₅-C₁₀cycloalkyl; and A is ZR; wherein the hydrocarbyl group is selected fromthe group consisting of: alkyl, cycloalkyl, aryl, aryalkyl, alkaryl,alkenyl, cycloalkenyl and alkynyl having from about 1 to 24 carbonatoms.
 7. The compound of claim 6, wherein R¹ is a H, C₁-C₄ alkyl, O,OH, C₁-C₁₈ alkoxy, C₁-C₁₈ hydroxyalkoxy, C₅-C₁₂ cycloalkoxy, C₅-C₁₂hydroxycycloalkoxy; R² is H, or C₁-C₄ alkyl; R³, R⁴, R⁵, and R⁶ are eachH or C₁-C₄ alkyl; R^(a), R^(b), R^(c), and R^(d), are each a hydrogen,alkyl, cycolalkyl, aryl, aryalkyl, alkaryl or alkenyl having from 1 to24 carbon atoms; and n is from 4 to
 11. 8. The compound of claim 6wherein R¹ is H or CH₃; R³, R⁴, R⁵, and R⁶ are each CH₃; R² is hydrogen;R^(a), R^(b), R^(c) and R^(d) are each a hydrogen; m is 0 or 1; and n isan integer from 4 to
 10. 9. The compound of claim 8 wherein n is 4.